CN112543750A

CN112543750A - Process for producing fluorinated secondary aromatic amine compound

Info

Publication number: CN112543750A
Application number: CN201980050340.6A
Authority: CN
Inventors: 小岛圭介
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2018-08-03
Filing date: 2019-08-01
Publication date: 2021-03-23
Anticipated expiration: 2039-08-01
Also published as: WO2020027258A1; CN116621715A; JP2023116505A; KR20210041579A; JPWO2020027258A1; JP2020063296A; CN112543750B; TW202031357A; JP6708319B1; JP2024003004A

Abstract

Using a catalyst comprising a palladium 0-valent complex of dibenzylideneacetone, a ligand represented by the following formula (L) and a baseA process for producing a fluorinated aromatic secondary amine compound by reacting a fluorinated aromatic primary amine compound with a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon, wherein a coupling reaction of the fluorinated aromatic amine compound with the chlorinated, brominated, or iodinated aromatic hydrocarbon or the pseudohalogenated aromatic hydrocarbon is carried out without using a special catalyst, whereby a secondary amine compound having a fluoroaryl moiety in the molecule can be produced easily and efficiently. (R)¹Each independently represents an alkyl group having 1 to 20 carbon atoms or the like, R²～R⁵Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, or the like, R⁶～R⁸Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )

Description

Process for producing fluorinated secondary aromatic amine compound

Technical Field

The present invention relates to a method for producing a fluorinated secondary aromatic amine compound.

Background

The reaction of cross-coupling an amine with a halide, pseudohalide to form a C-N bond using a palladium catalyst can be used for the synthesis of aromatic amines, the formation of heterocycles. This cross-coupling has become an important technique in a wide variety of fields such as the pharmaceutical field and the material field (non-patent document 1), and studies on catalysts used in the reaction and the reaction process have been widely conducted.

On the other hand, fluorine has the largest electronegativity among all elements, and therefore, when introduced into a molecule, the electronic state of the whole molecule can be changed greatly, and fluorine has not only the above-described characteristics but also the following characteristics: since the atomic radius is about the same as that of a hydrogen atom, even when a fluorine atom is introduced into a molecule instead of a hydrogen atom, the change in the size of the molecule is suppressed as compared with the case where other atoms or substituents are introduced.

Therefore, research on fluorides has been actively conducted, and many reports have been made on fluorides used for medicines and electronic materials. For example, in the field of electronic materials, it has been reported that an amine compound having a fluorine atom in the molecule is suitable as a charge transporting substance (patent document 1).

Under such circumstances, as a synthesis method of a fluoroaryl compound having an amino group, a reaction of an aromatic amine with a perfluoroarylboronic acid using copper acetate as a catalyst (non-patent document 2), a reaction of formanilide with perfluorobenzene in the presence of lithium hydroxide (non-patent document 3), a reaction of aniline with perfluorobenzene in the presence of t-BuONa (non-patent document 4), and the like have been reported, and in these reactions, the amino group as a reaction site is present on the side of an aromatic compound having no fluorine atom among 2 raw materials to be subjected to a coupling reaction.

For example, non-patent document 5 reports a method of coupling a fluoroarylamine compound and a haloaryl compound using a special palladium carbene complex as a catalyst, but has problems of high cost of the catalyst and low yield of the target product.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2008/032617

Non-patent document

Non-patent document 1: chem.Rev.2016,116,12564-12649

Non-patent document 2: angew. chem. int. ed.2014,53,3223

Non-patent document 3: journal of Fluorine Chemistry,74(2), 177-9; 1995

Non-patent document 4: RSC Advances,5(10),7035 and 7048; 2015

Non-patent document 5: angew. chem. int. ed.2014,53,3223

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for: a secondary amine compound having a fluoroaryl group in the molecule can be produced easily and efficiently by subjecting a fluorinated aromatic amine compound to a coupling reaction with a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon without using a special catalyst.

Means for solving the problems

The present inventors have made extensive studies to achieve the above object, and as a result, have found that: the present inventors have found that a coupling reaction between an amino group of a fluorinated aromatic amine compound and a chlorine atom, a bromine atom or an iodine atom or a pseudohalogen group of a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon is efficiently carried out in the presence of a predetermined palladium catalyst, a predetermined ligand and a base, and a secondary amine compound having a fluoroaryl moiety in the molecule is selectively obtained in a high yield, thereby completing the present invention.

Namely, the present invention provides:

1. a method for producing a fluorinated secondary aromatic amine compound, comprising the steps of: reacting a fluorinated aromatic primary amine compound with a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon in the presence of a catalyst, a ligand, and a base, characterized in that the catalyst comprises a palladium 0-valent complex of dibenzylidene acetone, and the ligand comprises a biphenylphosphine compound represented by the following formula (L),

[ solution 1]

(in the formula, R¹Each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R²～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R⁶～R⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or NR⁹ ₂Radical, R⁹Each independently represents an alkyl group having 1 to 20 carbon atoms. )

2.1A process for producing a fluorinated aromatic secondary amine compound, wherein the catalyst is a palladium 0-valent complex of dibenzylideneacetone, and the ligand is a biphenylphosphine compound represented by the formula (L),

3.1A process for producing a fluorinated secondary aromatic amine according to 1 or 2, wherein R is¹Each independently a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the carbon atom bonded to the phosphorus atom is a secondary or tertiary carbon atom,

4.3 the process for producing a fluorinated aromatic secondary amine, wherein R is¹Are both cyclohexyl or tert-butyl groups, and are,

5.1 to 4, wherein R represents a group represented by the formula²And R⁵Each independent earth surfaceA hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, wherein R is³And R⁴Are each a hydrogen atom, said R⁶～R⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms,

6.1 to 5, wherein the biphenylphosphine compound represented by the formula (L) is a biphenylphosphine compound represented by any one of the following formulae (L1) to (L4),

[ solution 2]

(wherein Me means methyl, i-Pr means isopropyl, Cy means cyclohexyl, and t-Bu means t-butyl.)

7.1 to 6, wherein the palladium 0-valent complex of dibenzylidene acetone is bis (dibenzylidene acetone) palladium (0),

8.1 to 7, wherein the fluorinated aromatic primary amine compound is a fluorinated aromatic primary monoamine compound or diamine compound having 2 or more fluorine atoms in the molecule,

9.1 to 8, wherein the chlorinated, brominated, or iodinated aromatic hydrocarbon is a monochloroaromatic hydrocarbon or a dichloroaromatic hydrocarbon, a monobromoaromatic hydrocarbon or a dibromoaromatic hydrocarbon, or a monoiodoaromatic hydrocarbon or a diiodoaromatic hydrocarbon,

10. a fluoroaniline derivative represented by the formula (T1) or (T2) (excluding compounds represented by the following formulae [1] to [13 ])

[ solution 3]

[ in the formula, X²¹¹Represents a 2-valent group represented by any one of formulae (A01-1) to (A09),

[ solution 4]

(in the formula, L⁰¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-, fluorene-9, 9-diyl, -NH-or-NZ¹⁰-，

L⁰²And L⁰³Each independently represents a hydrogen atom, may be Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²A substituted aryl group having 6 to 20 carbon atoms,

L⁰⁴represents a hydrogen atom, may be represented by Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²A substituted aryl group having 6 to 20 carbon atoms,

z' represents a substituent of an aromatic ring, each independently represents a substituent which may be substituted by Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²A substituted aryl group having 6 to 20 carbon atoms,

Z⁰¹～Z⁰⁹each independently represents a chlorine atom, a bromine atom, a nitro group, a cyano group, or a group which may be substituted by Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²A substituted aryl group having 6 to 20 carbon atoms,

Z¹⁰can be represented by Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²A substituted aryl group having 6 to 20 carbon atoms,

Z¹¹each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group or may be substituted by Z¹³A substituted aryl group having 6 to 20 carbon atoms,

Z¹²each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro groupCyano radicals, optionally substituted by Z¹³A substituted C1-20 alkyl group or Z¹³A substituted alkenyl group having 2 to 20 carbon atoms,

Z¹³represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group or a cyano group,

a¹¹、a¹³、a²¹、a²³、a³¹、a³³、a⁴¹、a⁵¹、a⁶¹、a⁷¹、a⁷³、a⁸¹、a⁸³、a⁹¹and a⁹³Represents the number of fluorine atoms substituted in the aromatic ring,

a¹²、a¹⁴、a²²、a²⁴、a³²、a³⁴、a⁴²、a⁵²、a⁶²、a⁷²、a⁷⁴、a⁸²、a⁸⁴、a⁹²and a⁹⁴Represents Z substituted on an aromatic ring⁰¹～Z⁰⁹The number of (a) or (b) is,

a⁷⁵and a⁷⁶Represents the number of Z' substituted on the aromatic ring,

a¹¹is an integer of 2 to 4, a¹²Is an integer of 0 to 2, and satisfies a¹¹+a¹²≤4，

a¹³Is an integer of 2 to 4, a¹⁴Is an integer of 0 to 2, and satisfies a¹³+a¹⁴≤4，

a²¹And a²³Each independently an integer of 1 to 4, a²²And a²⁴Each independently an integer of 0 to 3, and satisfies a²¹+a²²4 or less and a²³+a²⁴≤4，

a³¹And a³³Each independently an integer of 1 to 4, a³²And a³⁴Each independently an integer of 0 to 3, and satisfies a³¹+a³²4 or less and a³³+a³⁴≤4，

a⁴¹Is an integer of 1 to 6, a⁴²Is an integer of 0 to 5, and satisfies a⁴¹+a⁴²≤6，

a⁵¹Is an integer of 1 to 8, and,a⁵²is an integer of 0 to 7, and satisfies a⁵¹+a⁵²≤8，

a⁶¹Is an integer of 1 to 8, a⁶²Is an integer of 0 to 7, and satisfies a⁶¹+a⁶²≤8，

a⁷¹And a⁷³Each independently an integer of 1 to 3, a⁷²And a⁷⁴Each independently an integer of 0 to 2, and satisfies a⁷¹+a⁷²3 and a is ≤ 3 and⁷³+a⁷⁴≤3，a⁷⁵and a⁷⁶Each independently is an integer of 0 to 4,

a⁸¹and a⁸³Each independently an integer of 1 to 3, a⁸²And a⁸⁴Each independently an integer of 0 to 2, and satisfies a⁸¹+a⁸²3 and a is ≤ 3 and⁸³+a⁸⁴≤3，

a⁹¹and a⁹³Each independently an integer of 1 to 3, a⁹²And a⁹⁴Each independently an integer of 0 to 2, and satisfies a⁹¹+a⁹²3 and a is ≤ 3 and⁹³+a⁹⁴≤3。)

Y²¹¹and Y²¹²Each independently represents a 1-valent group represented by any one of formulae (B01) to (B21),

[ solution 5]

[ solution 6]

[ solution 7]

(in the formula, L¹¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-, fluorene-9, 9-diyl, -NH-or-NZ¹⁰⁰-，

L¹²Represents a hydrogen atom, may be represented by Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹³¹A substituted aryl group having 6 to 20 carbon atoms,

L¹³and L¹⁴Each independently represents a hydrogen atom, may be Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹³¹A substituted aryl group having 6 to 20 carbon atoms,

Z¹⁰⁰can be represented by Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹³¹A substituted aryl group having 6 to 20 carbon atoms,

Z¹⁰¹～Z¹⁰⁷and Z¹⁰⁹～Z¹²¹Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or a group which may be substituted by Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹³¹A substituted aryl group having 6 to 20 carbon atoms,

Z¹⁰⁸each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or a group which may be substituted by Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl with 2-20 carbon atoms or substituted alkenyl with Z¹³¹Substituted aryl group with 6-20 carbon atoms, Z existing on different benzene rings¹⁰⁸Can be combined to form a ring,

Z¹³⁰each independently represents a fluorine atom, a chlorine atom, a bromine atom or may be Z¹³²A substituted aryl group having 6 to 20 carbon atoms,

Z¹³¹each independently represents a fluorine atom, a chlorine atom, a bromine atom, or Z¹³²A substituted C1-20 alkyl group or Z¹³²A substituted alkenyl group having 2 to 20 carbon atoms,

Z¹³²represents a fluorine atom, a chlorine atom or a bromine atom,

Ar¹each independently represents an aryl group having 6 to 20 carbon atoms,

Ar²represents a single bond or an arylene group having 6 to 20 carbon atoms. )

X²²¹And X²²²Each independently represents a group having a valence of 1 represented by any one of formulae (C01) to (C09),

[ solution 8]

(in the formula, b¹¹、b²¹、b²³、b³¹、b³³、b⁴¹、b⁵¹、b⁶¹、b⁷¹、b⁷³、b⁸¹、b⁸³、b⁹¹And b⁹³Represents the number of fluorine atoms substituted in the aromatic ring,

b¹²、b²²、b²⁴、b³²、b³⁴、b⁴²、b⁵²、b⁶²、b⁷²、b⁷⁴、b⁸²、b⁸⁴、b⁹²and b⁹⁴Represents Z substituted on an aromatic ring⁰¹～Z⁰⁹The number of (a) or (b) is,

b⁷⁵and b⁷⁶Represents the number of Z' substituted on the aromatic ring,

b¹¹is an integer of 2 to 5, b¹²Is an integer of 0 to 3, and satisfies b¹¹+b¹²≤5，

b²¹Is an integer of 1 to 4, b²³Is an integer of 1 to 5, b²²Is an integer of 0 to 3, b²⁴Is an integer of 0 to 4, and satisfies b²¹+b²²4 or less and b²³+b²⁴≤5，

b³¹Is an integer of 1 to 4, b³³Is an integer of 1 to 5, b³²Is an integer of 0 to 3, b³⁴Is an integer of 0 to 4, and satisfies b³¹+b³²4 or less and b³³+b³⁴≤5，

b⁴¹Is an integer of 1 to 7, b⁴²Is an integer of 0 to 6, and satisfies b⁴¹+b⁴²≤7，

b⁵¹Is an integer of 1 to 9, b⁵²Is an integer of 0 to 8, and satisfies b⁵¹+b⁵²≤9，

b⁶¹Is an integer of 1 to 9, b⁶²Is an integer of 0 to 8, and satisfies b⁶¹+b⁶²≤9，

b⁷¹Is an integer of 1 to 3, b⁷³Is an integer of 1 to 4, b⁷²Is an integer of 0 to 2, b⁷⁴Is an integer of 0 to 3, and satisfies b⁷¹+b⁷²Less than or equal to 3 and b⁷³+b⁷⁴≤4，b⁷⁵And b⁷⁶Each independently an integer of 0 to 4,

b⁸¹is an integer of 1 to 3, b⁸³Is an integer of 1 to 4, b⁸²Is an integer of 0 to 2, b⁸⁴Is an integer of 0 to 3, and satisfies b⁸¹+b⁸²Less than or equal to 3 and b⁸³+b⁸⁴≤4，

b⁹¹Is an integer of 1 to 3, b⁹³Is an integer of 1 to 4, b⁹²Is an integer of 0 to 2, b⁹⁴Is an integer of 0 to 3, and satisfies b⁹¹+b⁹²Less than or equal to 3 and b⁹³+b⁹⁴≤4，

L⁰¹～L⁰⁴Z' and Z⁰¹～Z⁰⁷The same meanings as described above are indicated. )

Y²²¹Represents a 2-valent group represented by any one of formulae (D01-1) to (D21).

[ solution 9]

[ solution 10]

[ solution 11]

[ solution 12]

(wherein Ar is³Each independently represents an arylene group having 6 to 20 carbon atoms, L¹¹～L¹⁴、Z¹⁰¹～Z¹²¹And Ar¹The same meanings as described above are indicated. )]

[ solution 13]

11.10 fluorine-containing aniline derivative, wherein X is²¹¹Is a 2-valent group represented by the formula (A02),

12.11 fluorine-containing aniline derivative, wherein X²¹¹Is a 2-valent group represented by the following formula (A02-1):

[ solution 14]

(in the formula, a)²¹～a²⁴And Z⁰²The same meanings as described above are indicated. )

13.10 to 12, wherein Y is²¹¹And Y²¹²Are the same group of valency 1,

14.13 fluorine-containing aniline derivative, wherein Y is²¹¹And Y²¹²Are each a 1-valent group represented by any one of the formulae (B01), (B02), (B04), (B08) and (B18),

15.10 fluorine-containing aniline derivative, wherein Y is²²¹Is a 2-valent group represented by the formula (D02),

16.15 the fluoroaniline derivative wherein Y is²²¹Is a 2-valent group represented by the following formula (D02-1):

[ solution 15]

17.10, 15 or 16 of fluoroaniline derivatives wherein X²²¹And X²²²Are the same group of valency 1,

18.17 fluorine-containing aniline derivative wherein X²²¹And X²²²Are each a group having a valence of 1 represented by the above formula (C01),

19. a polymer comprising a repeating unit represented by the following formula (P1-2):

[ solution 16]

[ solution 17]

L⁰⁴represents a hydrogen atom, may be represented by Z¹¹Substituted carbonAlkyl of number 1-20, optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²A substituted aryl group having 6 to 20 carbon atoms,

Z¹²each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or Z¹³A substituted C1-20 alkyl group or Z¹³A substituted alkenyl group having 2 to 20 carbon atoms,

a⁷⁵and a⁷⁶Represents the number of Z' substituted on the aromatic ring,

a⁵¹Is an integer of 1 to 8, a⁵²Is an integer of 0 to 7, and satisfies a⁵¹+a⁵²≤8，

[ solution 18]

[ solution 19]

[ solution 20]

[ solution 21]

(in the formula, L¹¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-, fluorene-9, 9-diyl, -NH-or-NZ⁰²-，

L¹³and L¹⁴Each independently represents a hydrogen atom, may be Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹³¹Substituted byAn aryl group having 6 to 20 carbon atoms,

Z¹³²represents a fluorine atom, a chlorine atom or a bromine atom,

Ar¹each independently represents an aryl group having 6 to 20 carbon atoms,

Ar³each independently represents an arylene group having 6 to 20 carbon atoms. )]

20.19 polymers of wherein X²¹¹Is a 2-valent group represented by the above formula (A02),

21.20 of the polymers, wherein, X²¹¹Is a 2-valent group represented by the following formula (A02-1),

[ solution 22]

(in the formula, a)²¹～a²⁴And Z⁰²Represents the same as aboveAnd (5) defining. )

22.19 to 21, wherein Y is²²¹Is a 2-valent group represented by any one of the above-mentioned formulae (D02), (D17) and (D19),

23. a charge transporting substance comprising an aniline derivative of any one of 10 to 18,

24. a charge transporting material comprising a polymer of any one of 19 to 22,

25. a charge transporting composition comprising the charge transporting substance of 23 or 24 and an organic solvent,

26.25 of a charge transporting composition comprising a dopant species,

27. a charge transport film obtained from the charge transport composition of 25 or 26,

28. an electronic component comprising the charge transporting thin film of 27,

29. an organic electroluminescent element comprising a charge transporting thin film of 27,

30.29, wherein the charge transporting thin film is a hole injecting layer or a hole transporting layer.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the method for producing a fluorinated aromatic secondary amine compound of the present invention, a secondary amine compound having a fluoroaryl moiety in the molecule (fluoroaniline derivative) can be produced efficiently and at high yield and at low cost from a fluorinated aromatic amine compound and a chlorinated, brominated, or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon using a commercially available palladium catalyst and a ligand having a biphenyl skeleton.

In addition, in this reaction, polymerization proceeds by using a 2-functional compound as the fluorinated aromatic amine compound and the chlorinated, brominated, or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon, and a polymer such as an oligoaniline derivative or a polyaniline derivative having a fluoroaryl moiety in the molecule can be efficiently produced.

The fluorinated amine compound such as the fluorinated aniline derivative or the polymer obtained by the production method of the present invention has fluorine atoms in the molecule, and therefore has excellent transparency and exhibits charge transport properties, and therefore, it can be suitably used as a material for forming a charge-transporting thin film for electronic devices such as organic EL devices by itself or in combination with other charge-transporting materials or dopant substances.

Detailed Description

The present invention is described in more detail below.

[1] Process for producing fluorinated secondary aromatic amine compound

The method for producing a fluorinated secondary aromatic amine compound according to the present invention comprises the steps of: a fluorinated primary aromatic amine compound is reacted with a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon in the presence of a catalyst, a ligand, and a base.

(1) Catalyst and process for preparing same

The catalyst used in the present invention comprises a palladium 0-valent complex of dibenzylidene acetone.

Specific examples of the palladium 0-valent complex of dibenzylideneacetone include bis (dibenzylideneacetone) palladium (0), tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) (chloroform) dipalladium (0), and among these, bis (dibenzylideneacetone) palladium (0) is preferable.

The amount of the palladium 0-valent complex of dibenzylideneacetone to be used is not particularly limited as long as the intended coupling reaction proceeds, and is preferably 0.0001 to 0.2mol, more preferably 0.005 to 0.15mol, further preferably 0.01 to 0.12mol, and further preferably 0.02 to 0.1mol, based on the palladium metal, relative to 1mol of NH at the amine site of the fluorinated aromatic primary amine compound.

In the present invention, other metal catalysts may be used together with the palladium 0-valent complex of dibenzylideneacetone within a range not to impair the effects of the present invention.

Examples of the other metal catalyst include copper catalysts such as copper chloride, copper bromide, and copper iodide; pd (PPh)₃)₄(tetrakis (triphenylphosphine) palladium), Pd (PPh)₃)₂Cl₂(bis (triphenylphosphine) palladium dichloride), Pd (P-t-Bu)₃)₂(bis (tris (t-butylphosphino)) palladium), Pd (OAc)₂(Palladium acetate), etcPalladium catalysts, and the like.

When these other metal catalysts are used, the amount thereof cannot be generally specified, and is usually less than 100 mol% based on the palladium 0-valent complex of dibenzylideneacetone.

(2) Ligands

The ligand used in the present invention contains a biphenylphosphine compound represented by the following formula (L).

[ solution 23]

In the formula (L), R¹Each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R²～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R⁶～R⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or NR⁹ ₂Radical, R⁹Each independently represents an alkyl group having 1 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include straight-chain, branched-chain and cyclic alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl and eicosyl groups; and C3-20 cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, and adamantyl.

Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl.

Specific examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a c-propoxy group (cyclopropoxy group), a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentoxy group, a n-hexoxy group, a n-heptoxy group, a n-octoxy group, a n-nonoxy group, and a n-decyloxy group.

Among these, R is R from the viewpoint of obtaining the target with good reproducibility¹Each independently preferably has a relatively large volume, preferably has a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, wherein the carbon atom at the bonding end is a secondary carbon atom or a tertiary carbon atom, more preferably has a branched alkyl group having 3 to 5 carbon atoms, a cyclic alkyl group having 5 to 7 carbon atoms, and further preferably has a tert-butyl group or a cyclohexyl group, from the viewpoint of solubility in a solvent and stability.

Furthermore, from the viewpoint of ease of synthesis, 2R's are preferred¹The same is true.

In addition, from the viewpoint of stability of the compound and the viewpoint of obtaining an object with good reproducibility, R is²～R⁵Each independently preferably represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, more preferably R²And R⁵Each independently represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, R³And R⁴All are combinations of hydrogen atoms, and R is more preferably²～R⁵All are hydrogen atoms.

Further, from the viewpoint of stability of the compound and the viewpoint of obtaining a target product with good reproducibility, R is⁶～R⁸The alkyl group is preferably a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms wherein the carbon atom at the bonding end is a primary carbon atom or a secondary carbon atom, or an alkoxy group having 1 to 20 carbon atoms, more preferably a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and further preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxy group, or an isopropoxy group, from the viewpoints of solubility in a solvent and stability.

In particular, as R⁶And R⁸Preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a methyl group, an isopropyl group, a methyl group, an ethyl,Methoxy group, isopropoxy group.

As R⁷The alkyl group is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or an isopropyl group.

The ligand preferably used in the present invention includes ligands represented by the following formulae (L1) to (L7), but is not limited thereto.

[ solution 24]

(wherein Me means methyl, i-Pr means isopropyl, t-Bu means t-butyl, and Cy means cyclohexyl.)

The ligand represented by the formula (L) is commercially available, and examples thereof include John Phos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavePhos, PhDavePhos, 2' -dicyclohexylphosphino-2, 4, 6-trimethoxybiphenyl, BrettPhos, tBuBrettPos, AdBrettPos, Me as Buchwald ligand and the like which are commercially available from Aldrich Co₃(OMe) tBuXPhos, (2-biphenyl) di-1-adamantylphosphine, RockPhos, CPhos, and the like.

The ligand represented by the formula (L) can be synthesized by a known method.

The amount of the ligand represented by the formula (L) used is preferably 1 to 2 equivalents based on the catalyst used. In particular, when the amount is less than 1 equivalent, palladium black may be generated.

In the present invention, other ligands may be used together with the ligand represented by the formula (L) within a range not impairing the effects of the present invention.

Specific examples of the other ligands include tertiary phosphines such as triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine, di-t-butyl (phenyl) phosphine, di-t-butyl (4-dimethylaminophenyl) phosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1' -bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, and the like.

When another ligand is used, the amount of the ligand to be used is not generally specified, and is usually less than 100 mol% based on the ligand represented by the formula (L).

(3) Fluorinated primary aromatic amine compounds

In the production method of the present invention, the fluorinated primary aromatic amine compound as a raw material to be used in the coupling reaction is not particularly limited because of the characteristics of the above-mentioned catalyst and ligand.

The fluorinated aromatic primary amine compound may be a monoamine compound or a diamine compound, and examples thereof include compounds represented by the following formulae (X1) and (X2).

[ solution 25]

Ar^F1-NH₂ (X1) H₂N-Ar^F2-NH₂ (X2)

(wherein Ar is^F1Represents a fluorinated aryl group, Ar^F2Represents a fluorinated arylene group. )

The fluorinated aryl group may be one in which at least 1 hydrogen atom of the aryl group is replaced by a fluorine atom, and preferably 2 or more hydrogen atoms are replaced by a fluorine atom.

The fluorinated arylene group may be one in which at least 1 hydrogen atom of the arylene group is replaced by a fluorine atom, and preferably 2 or more hydrogen atoms are replaced by a fluorine atom.

That is, the fluorinated aromatic primary amine compound used in the present invention is preferably a fluorinated aromatic primary monoamine compound or diamine compound having 2 or more fluorine atoms in the molecule.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group; 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-tetracenyl, 2-tetracenyl, 5-tetracenyl, 2-

A group consisting of 1-pyrenyl, 2-pyrenyl, pentacenyl, benzopyrenyl, benzo [9,10 ]]Phenanthryl and the like fused ring aromatic hydrocarbonsA group derived by removing one of hydrogen atoms on an aromatic ring of a compound; biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, m-terphenyl-4-yl, o-terphenyl-4-yl, 1 '-binaphthyl-2-yl, 2' -binaphthyl-1-yl, and the like, and groups derived by removing one of the hydrogen atoms on the aromatic ring of the cyclic hydrocarbon compound.

The arylene group is preferably an arylene group having 6 to 20 carbon atoms, and specific examples thereof include a1, 2-phenylene group, a1, 3-phenylene group, a1, 4-phenylene group; 1, 5-naphthylene group, 1, 8-naphthylene group, 2, 6-naphthylene group, 2, 7-naphthylene group, 1, 2-anthrylene group, 1, 3-anthrylene group, 1, 4-anthrylene group, 1, 5-anthrylene group, 1, 6-anthrylene group, 1, 7-anthrylene group, 1, 8-anthrylene group, 2, 3-anthrylene group, 2, 6-anthrylene group, 2, 7-anthrylene group, 2, 9-anthrylene group, 2, 10-anthrylene group, 9, 10-anthrylene group, and the like, which are derived by removing two hydrogen atoms from the aromatic ring of the fused ring aromatic hydrocarbon compound; biphenyl-4, 4' -diyl, p-terphenyl-4, 4 "-diyl, and the like are groups derived by removing two hydrogen atoms from the aromatic ring of the cyclic hydrocarbon compound.

(4) Chlorinated, brominated or iodinated aromatic or pseudohalogenated aromatic hydrocarbons

The chlorinated, brominated, iodinated or pseudohalogenated aromatic hydrocarbon may be a compound having 1 reaction site reacting with an amino group of a fluorinated aromatic primary amine, such as a monochloro, monobromo, monoiodo or monopseudohalogen compound, or a compound having 2 or more reaction sites reacting with an amino group of a fluorinated aromatic primary amine, such as a dichloro, dibromo, diiodo or bispseudohalogen compound, and examples thereof include compounds represented by the following formulae (Y1) and (Y2).

[ solution 26]

Ar⁴-X (Y1) X-Ar⁵-X (Y2)

(wherein Ar is⁴Represents aryl, Ar⁵Represents an arylene group, and each X independently represents a chlorine atom, a bromine atom, an iodine atom or a pseudohalogen group. )

Examples of the aryl group and the arylene group include the same groups as described above.

Examples of the pseudohalogen group include (fluoro) alkylsulfonyloxy groups such as methylsulfonyloxy, trifluoromethanesulfonyloxy and nonafluorobutanesulfonyloxy; and aromatic sulfonyloxy groups such as benzenesulfonyloxy and toluenesulfonyloxy.

X is preferably a bromine atom or an iodine atom from the viewpoint of reactivity.

In particular, the chlorinated, brominated or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon used in the present invention is preferably a monochloroacetic or dichloroaromatic hydrocarbon, a monobromoacetic or dibromoaromatic hydrocarbon, or a monoiodogenic or diiodogenic aromatic hydrocarbon, more preferably a monobromoacetic or dibromoaromatic hydrocarbon, or a monoiodogenic or diiodogenic aromatic hydrocarbon.

(5) Alkali

The base is also not particularly limited, and examples thereof include simple alkali metals such as lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate and the like, hydrogenated alkali metals, alkali metals hydroxide, alkali metals alkoxide, alkali metals carbonate, alkali metals hydrogencarbonate; alkali earth carbonate metals such as calcium carbonate; organolithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, Lithium Diisopropylamide (LDA), lithium 2, 2, 6, 6-tetramethylpiperidine (LiTMP), Lithium Hexamethyldisilazane (LHMDS); amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine, etc., but lithium amide reagents for lithiating secondary amines such as LDA, LiTMP, and LHMDS, and alkali metal alkoxides such as lithium tert-butoxide, etc., are preferable.

(6) Coupling reaction

In the production process of the present invention, the NH relative to the fluorinated aromatic primary amine compound with respect to the feed ratio of the fluorinated aromatic primary amine compound to the chlorinated, brominated or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon₂The reaction site of chlorine, bromine, iodine or pseudohalogen as an aromatic hydrocarbon is preferably about 1.0 to 1.2 mol based on 1mol of the base.

For example, in the reaction of formula (X1) and formula (Y1), about 1 to 1.2 is preferable for (X1) and (Y1) of 1, about 0.5 to 0.6 is preferable for (X1) and (Y1) of 1 in the reaction of formula (X1) and (Y2), about 2 to 2.4 is preferable for (X2) and (Y1) of 1 in the reaction of formula (X2) and formula (Y1), and about 1 to 1.2 is preferable for (X2) and (Y2) of 1 in the reaction of formula (X2) and (Y2), as expressed by the amount (molar) ratio of the substance.

The coupling reaction of the present invention is carried out in a solvent in the case where all of the starting compounds are solid or from the viewpoint of efficiently obtaining the objective fluorinated secondary aromatic amine compound.

When a solvent is used, the kind thereof is not particularly limited as long as it does not adversely affect the reaction. Specific examples thereof include aliphatic hydrocarbons (e.g., pentane, N-hexane, N-octane, N-decane, decalin), halogenated aliphatic hydrocarbons (e.g., chloroform, dichloromethane, dichloroethane, and carbon tetrachloride), aromatic hydrocarbons (e.g., benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene), halogenated aromatic hydrocarbons (e.g., chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene), ethers (e.g., diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, 1, 2-dimethoxyethane, 1, 2-diethoxyethane), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, di-N-butyl ketone, and cyclohexanone), amides (e.g., N-dimethylformamide and N, N-dimethylacetamide), lactams, and lactones (e.g., N-methylpyrrolidone), γ -butyrolactone, etc.), ureas (N, N-dimethylimidazolidinone, tetramethylurea, etc.), sulfoxides (dimethyl sulfoxide, sulfolane, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.), etc., and these solvents may be used alone or in combination of 2 or more.

In particular, in the present invention, as the solvent, ethers are preferably used, and dioxane is more preferably used.

The lower limit of the reaction temperature varies depending on the reactivity of the reaction substrate, and therefore cannot be generally specified, and if it is 45 ℃ or higher, the coupling reaction proceeds well in general. In particular, if considering further improvement in reactivity, the reaction temperature is preferably 60 ℃ or more, more preferably 75 ℃ or more, further preferably 90 ℃ or more, and particularly, the reaction is preferably carried out under heating reflux of the solvent. On the other hand, the upper limit of the reaction temperature varies depending on the boiling point of the solvent used, and therefore cannot be generally specified, and is usually about 200 ℃ or lower.

After the reaction is completed, the desired fluorinated secondary aromatic amine compound can be obtained by post-treatment according to a conventional method.

[2] Fluorine-containing aniline derivative

One of the fluorine-containing aniline derivatives according to the present invention is represented by the following formula (T1).

[ solution 27]

In the above formula (T1), X²¹¹Represents a 2-valent group represented by any one of formulas (A01-1) to (A09).

[ solution 28]

Wherein L is⁰¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-, fluorene-9, 9-diyl, -NH-or-NZ¹⁰-。

L⁰²And L⁰³Each independently represents a hydrogen atom, may be Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²The substituted aryl group having 6 to 20 carbon atoms is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms, and more preferably a hydrogen atom, a methyl group or a phenyl group.

Specific examples of the alkyl group and the aryl group include the same groups as described above.

Specific examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, n-1-propenyl, n-2-propenyl, 1-methylvinyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n-1-eicosenyl and the like.

L⁰⁴Represents a hydrogen atom, may be represented by Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²Examples of the substituted aryl group having 6 to 20 carbon atoms include the same ones as described above as the alkyl group, the alkenyl group and the aryl group. In these, L⁰⁴Preferably a hydrogen atom or a phenyl group.

Z' represents a substituent of an aromatic ring, each independently represents a substituent which may be substituted by Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²Examples of the substituted aryl group having 6 to 20 carbon atoms include the same ones as described above as the alkyl group, the alkenyl group and the aryl group.

Z⁰¹～Z⁰⁹Each independently represents a chlorine atom, a bromine atom, a nitro group, a cyano group, or a group which may be substituted by Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²Substituted aryl group having 6 to 20 carbon atoms, Z¹⁰Can be represented by Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²Substituted aryl group having 6 to 20 carbon atoms, Z¹¹Each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group or may be substituted by Z¹³Substituted aryl group having 6 to 20 carbon atoms, Z¹²Each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or Z¹³A substituted C1-20 alkyl group or Z¹³A substituted alkenyl group having 2 to 20 carbon atoms, Z¹³The alkyl group may be a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group or a cyano group, and specific examples of the alkyl group, the alkenyl group and the aryl group include the same groups as described above.

Wherein, in Z⁰¹～Z⁰⁹When present, nitro or C1-5 alkyl which may be substituted with fluorine atom is preferable. In addition, Z¹⁰Phenyl which may be substituted by fluorine atoms is preferred.

Further, a substituent Z in the aromatic ring^pWhen a plurality of (p ═ 01 to 09) are present, they may be the same or different from each other.

a¹¹、a¹³、a²¹、a²³、a³¹、a³³、a⁴¹、a⁵¹、a⁶¹、a⁷¹、a⁷³、a⁸¹、a⁸³、a⁹¹And a⁹³Denotes the number of fluorine atoms substituted in the aromatic ring, a¹²、a¹⁴、a²²、a²⁴、a³²、a³⁴、a⁴²、a⁵²、a⁶²、a⁷²、a⁷⁴、a⁸²、a⁸⁴、a⁹²And a⁹⁴Represents Z substituted on an aromatic ring⁰¹～Z⁰⁹A number of⁷⁵And a⁷⁶Represents the number of Z' substituted on the aromatic ring.

a¹¹Is an integer of 2 to 4, a¹²Is an integer of 0 to 2, and satisfies a¹¹+a¹²≤4。

a¹³Is an integer of 2 to 4, a¹⁴Is an integer of 0 to 2, and satisfies a¹³+a¹⁴≤4。

a²¹And a²³Each independently an integer of 1 to 4, a²²And a²⁴Each independently an integer of 0 to 3, and satisfies a²¹+a²²4 or less and a²³+a²⁴≤4。

a³¹And a³³Each independently an integer of 1 to 4, a³²And a³⁴Each independently an integer of 0 to 3, and satisfies a³¹+a³²4 or less and a³³+a³⁴≤4。

a⁴¹Is an integer of 1 to 6, a⁴²Is an integer of 0 to 5, and satisfies a⁴¹+a⁴²≤6。

a⁵¹Is an integer of 1 to 8, a⁵²Is an integer of 0 to 7, and satisfies a⁵¹+a⁵²≤8。

a⁶¹Is an integer of 1 to 8, a⁶²Is an integer of 0 to 7, and satisfies a⁶¹+a⁶²≤8。

a⁷¹And a⁷³Each independently an integer of 1 to 3, a⁷²And a⁷⁴Each independently an integer of 0 to 2, and satisfies a⁷¹+a⁷²3 and a is ≤ 3 and⁷³+a⁷⁴≤3，a⁷⁵and a⁷⁶Each independently is an integer of 0 to 4.

a⁸¹And a⁸³Each independently an integer of 1 to 3, a⁸²And a⁸⁴Each independently an integer of 0 to 2, and satisfies a⁸¹+a⁸²3 and a is ≤ 3 and⁸³+a⁸⁴≤3。

a⁹¹and a⁹³Each independently an integer of 1 to 3, a⁹²And a⁹⁴Each independently an integer of 0 to 2, and satisfies a⁹¹+a⁹²3 and a is ≤ 3 and⁹³+a⁹⁴≤3。

in particular, a⁴¹、a⁵¹、a⁶¹Preferably an integer of 2 or more.

In addition, a¹²、a¹⁴、a²²、a²⁴、a³²、a³⁴、a⁴²、a⁵²、a⁶²、a⁷²、a⁷⁴、a⁸²、a⁸⁴、a⁹²And a⁹⁴Preferably 0, a⁷⁵And a⁷⁶Preferably 0.

In these, X²¹¹The group having a valence of 2 represented by the formula (A02) is preferable, the group having a valence of 2 represented by the following formula (A02-1) is more preferable, and if it is considered to be used as a charge transporting substance, the perfluorobiphenylene group represented by the formula (A02-1-1) is further preferable.

[ solution 29]

(in the formula, a)²¹～a²⁴And Z⁰²Is shown and described aboveThe same meaning is used. )

[ solution 30]

On the other hand, Y²¹¹And Y²¹²Each independently represents a 1-valent group represented by any one of formulae (B01) to (B21).

[ solution 31]

[ solution 32]

[ solution 33]

Wherein L is¹¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-, fluorene-9, 9-diyl, -NH-or-NZ¹⁰⁰-。

L¹²Represents a hydrogen atom, may be represented by Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹³¹Examples of the substituted aryl group having 6 to 20 carbon atoms include the same ones as described above as the alkyl group, the alkenyl group and the aryl group. In these, L¹²Preferably a hydrogen atom or a phenyl group.

L¹³And L¹⁴Each independently represents a hydrogen atom, may be Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹³¹Substituted carbon number 6EExamples of the aryl group of 20 include the same ones as described above as the alkyl group, the alkenyl group and the aryl group. Among these, as L¹³And L¹⁴The alkyl group is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably a hydrogen atom, a methyl group or a phenyl group.

Z¹⁰⁰Can be represented by Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹³¹The substituted aryl group having 6 to 20 carbon atoms is preferably a phenyl group which may be substituted with a fluorine atom.

Z¹⁰¹～Z¹⁰⁷And Z¹⁰⁹～Z¹²¹Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or a group which may be substituted by Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹³¹Substituted aryl group having 6 to 20 carbon atoms, Z¹⁰⁸Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or a group which may be substituted by Z¹³⁰A substituted C1-20 alkyl group optionally substituted by Z¹³⁰Substituted alkenyl with 2-20 carbon atoms or substituted alkenyl with Z¹³¹Substituted aryl group having 6 to 20 carbon atoms, wherein Z is present on different benzene rings¹⁰⁸May combine to form a ring, Z¹³⁰Each independently represents a fluorine atom, a chlorine atom, a bromine atom or may be Z¹³²Substituted aryl group having 6 to 20 carbon atoms, Z¹³¹Each independently represents a fluorine atom, a chlorine atom, a bromine atom, or Z¹³²A substituted C1-20 alkyl group or Z¹³²A substituted alkenyl group having 2 to 20 carbon atoms, Z¹³²The alkyl group may be a linear alkyl group, or a linear alkyl group. In these, Z¹⁰¹～Z¹⁰⁷And Z¹⁰⁹～Z¹²¹Preferably a hydrogen atom. Z¹⁰⁸Preferably hydrogen atoms or at least 1 group Z which is present on different phenyl rings in ortho position to the nitrogen atom¹⁰⁸A single bond bonded therebetween. Further, as Z¹⁰⁸Examples of the formula (B08) having a single bond formed therebetween include a structure represented by the following formula (B08').

Furthermore, Z^q(q is 101 to 121) may be the same or different.

[ chemical 34]

Ar¹Each independently represents an aryl group having 6 to 20 carbon atoms, and examples of the aryl group include the same aryl groups as described above. Wherein Ar is¹Phenyl, 1-naphthyl and 2-naphthyl are preferred, and phenyl is more preferred.

Ar²Represents a single bond or an arylene group having 6 to 20 carbon atoms. Specific examples of the arylene group having 6 to 20 carbon atoms include 1, 2-phenylene, 1, 3-phenylene, 1, 4-phenylene, 1, 5-naphthylene, 1, 8-naphthylene, 2, 6-naphthylene, 2, 7-naphthylene and the like. Wherein Ar is²Single bond, 1, 4-phenylene group is preferred.

Particularly, if ease of synthesis and the like are taken into consideration, Y is preferable²¹¹And Y²¹²The same 1-valent group is more preferably a 1-valent group each represented by any one of formulae (B01), (B02), (B04), (B08), and (B18).

Another fluorinated aniline derivative according to the present invention is represented by the following formula (T2).

[ solution 35]

In the formula (T2), X²²¹And X²²²Each independently represents a 1-valent group represented by any one of formulae (C01) to (C09).

[ solution 36]

Wherein, b¹¹、b²¹、b²³、b³¹、b³³、b⁴¹、b⁵¹、b⁶¹、b⁷¹、b⁷³、b⁸¹、b⁸³、b⁹¹And b⁹³Represents the number of fluorine atoms substituted in the aromatic ring, b¹²、b²²、b²⁴、b³²、b³⁴、b⁴²、b⁵²、b⁶²、b⁷²、b⁷⁴、b⁸²、b⁸⁴、b⁹²And b⁹⁴Represents Z substituted on an aromatic ring⁰¹～Z⁰⁹A number of (b)⁷⁵And b⁷⁶Represents the number of Z' substituted on the aromatic ring.

b¹¹Is an integer of 2 to 5, b¹²Is an integer of 0 to 3, and satisfies b¹¹+b¹²≤5。

b²¹Is an integer of 1 to 4, b²³Is an integer of 1 to 5, b²²Is an integer of 0 to 3, b²⁴Is an integer of 0 to 4, and satisfies b²¹+b²²4 or less and b²³+b²⁴≤5。

b³¹Is an integer of 1 to 4, b³³Is an integer of 1 to 5, b³²Is an integer of 0 to 3, b³⁴Is an integer of 0 to 4, and satisfies b³¹+b³²4 or less and b³³+b³⁴≤5。

b⁴¹Is an integer of 1 to 7, b⁴²Is an integer of 0 to 6, and satisfies b⁴¹+b⁴²≤7。

b⁵¹Is an integer of 1 to 9, b⁵²Is an integer of 0 to 8, and satisfies b⁵¹+b⁵²≤9。

b⁶¹Is an integer of 1 to 9, b⁶²Is an integer of 0 to 8, and satisfies b⁶¹+b⁶²≤9。

b⁷¹Is an integer of 1 to 3, b⁷³Is an integer of 1 to 4, b⁷²Is an integer of 0 to 2, b⁷⁴Is an integer of 0 to 3, and satisfies b⁷¹+b⁷²Less than or equal to 3 and b⁷³+b⁷⁴≤4，b⁷⁵And b⁷⁶Each independently an integer of 0 to 4.

b⁸¹Is an integer of 1 to 3，b⁸³Is an integer of 1 to 4, b⁸²Is an integer of 0 to 2, b⁸⁴Is an integer of 0 to 3, and satisfies b⁸¹+b⁸²Less than or equal to 3 and b⁸³+b⁸⁴≤4。

b⁹¹Is an integer of 1 to 3, b⁹³Is an integer of 1 to 4, b⁹²Is an integer of 0 to 2, b⁹⁴Is an integer of 0 to 3, and satisfies b⁹¹+b⁹²Less than or equal to 3 and b⁹³+b⁹⁴≤4。

In particular, b⁴¹、b⁵¹、b⁶¹Preferably an integer of 2 or more.

In addition, b¹²、b²²、b²⁴、b³²、b³⁴、b⁴²、b⁵²、b⁶²、b⁷²、b⁷⁴、b⁸²、b⁸⁴、b⁹²And b⁹⁴Preferably 0, b⁷⁵And b⁷⁶Preferably 0.

Note that L is⁰¹～L⁰⁴Z' and Z⁰¹～Z⁰⁹The same meanings as described above are indicated.

In particular, if ease of synthesis, charge transport property, etc. are taken into consideration, X²²¹And X²²²The same 1-valent groups are preferred, and all 1-valent groups represented by the formula (C01) are more preferred, and all 1-valent groups represented by the following formula (C01-1) are even more preferred.

[ solution 37]

On the other hand, Y²²¹Represents a 2-valent group represented by any one of formulae (D01-1) to (D21).

[ solution 38]

[ solution 39]

[ solution 40]

[ solution 41]

In the formula, Ar³Each independently represents an arylene group having 6 to 20 carbon atoms, and specific examples of the arylene group include those similar to the above.

In addition, L¹¹～L¹⁴、Z¹⁰¹～Z¹²¹And Ar¹The same meanings as described above are indicated.

In these, Y²²¹The group having a valence of 2 represented by the formula (D02) is preferable, the group having a valence of 2 represented by the following formula (D02-1) is more preferable, and the biphenylene group represented by the following formula (D02-1-1) is further preferable.

[ solution 42]

(in the formula, Z¹⁰²The same meanings as described above are indicated. )

Furthermore, the fluorinated aniline derivative of the present invention does not contain compounds represented by the following formulas [1] to [13 ].

[ solution 43]

Specific examples of the fluorine-containing aniline derivative of the present invention include, but are not limited to, compounds represented by the following formulae.

[ solution 44]

(wherein t-Bu represents a tert-butyl group.)

[3] Polymer and method of making same

The polymer of the present invention comprises a repeating unit represented by the following formula (P1-2).

[ solution 45]

In the formula (P1-2), X²¹¹The same groups as exemplified above for the fluorinated aniline derivative are exemplified, and the preferred ranges are the same as described above.

In addition, Y²²¹The same groups as those exemplified for the fluorinated aniline derivative may be mentioned, and among them, a 2-valent group represented by any one of the formulae (D02), (D17) and (D19) is preferable.

The molecular weight of the polymer of the present invention is not particularly limited, but considering conductivity when used as a charge transporting substance, solubility in an organic solvent, and the like, the weight average molecular weight is preferably 1000 to 100000, more preferably 2000 to 50000, and further preferably 5000 to 30000. The weight average molecular weight is a polystyrene equivalent value obtained by gel permeation chromatography.

Specific examples of the polymer of the present invention include, but are not limited to, those represented by the following formulae.

[ solution 46]

(wherein m independently represents an integer of 2 or more.)

[4] Process for producing fluorine-containing aniline derivative and polymer

The fluorinated aniline derivative and the polymer of the present invention described above can be synthesized by the above-described method for producing a fluorinated secondary aromatic amine of the present invention.

For example, the fluorine-containing aniline derivative can be obtained by reacting a fluorinated aromatic primary diamine represented by the above formula (X2) with 2 equivalents of a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon represented by the above formula (Y1) in the presence of a palladium 0-valent complex of dibenzylideneacetone, a ligand represented by the above formula (L), and a base, or reacting a fluorinated aromatic primary amine represented by the above formula (X1) with 0.5 equivalents of a dichloroaromatic hydrocarbon, a dibrominated aromatic hydrocarbon, or a diiodonated aromatic hydrocarbon or a dibrominated aromatic hydrocarbon represented by the above formula (Y2).

On the other hand, the polymer can be obtained by reacting a fluorinated aromatic primary diamine compound represented by the above formula (X2) with a dichloroaromatic hydrocarbon, a dibrominated aromatic hydrocarbon or a diiodoated aromatic hydrocarbon or a dihalogenated aromatic hydrocarbon represented by the above formula (Y2) in the presence of a palladium 0-valent complex of dibenzylideneacetone, a ligand represented by the above formula (L) and a base. Further, in the synthesis of a polymer, since the molecular weight is increased by increasing the amount of the catalyst, the molecular weight of the polymer to be obtained can be adjusted by adjusting the amount of the catalyst.

[5] Charge-transporting substance, charge-transporting composition, and charge-transporting film

The fluorinated aniline derivative and the polymer of the present invention have fluorine atoms in the molecule, and therefore have excellent transparency, and exhibit conductivity alone or in combination with a dopant substance, and therefore can be preferably used as a charge transporting substance.

For example, the charge transporting composition of the present invention includes a composition containing a charge transporting substance composed of the above fluorine-containing aniline derivative or polymer and an organic solvent, and may contain a dopant substance for the purpose of, for example, improving the charge transporting ability of the resulting thin film, depending on the application.

The dopant substance is not particularly limited as long as it is dissolved in at least one solvent used in the composition.

Specific examples of the dopant substance include inorganic strong acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid; aluminium (III) chloride (AlCl)₃) Titanium tetrachloride (IV) (TiCl)₄) Boron tribromide (BBr)₃) Boron trifluoride ether complex (BF)₃·OEt₂) Iron (III) chloride (FeCl)₃) Copper (II) chloride (CuCl)₂) Antimony (V) pentachloride (SbCl)₅) Arsenic (V) pentafluoride (AsF)₅) Phosphorus Pentafluoride (PF)₅) Lewis acids such as tris (4-bromophenyl) aluminum hexachloroantimonate (TBPAH); organic strong acids such as naphthalenedisulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, dodecylbenzenesulfonic acid and 1, 5-naphthalenedisulfonic acid, naphthalenetrisulfonic acids such as 1,3, 5-naphthalenetrisulfonic acid and 1,3, 6-naphthalenetrisulfonic acid, polystyrenesulfonic acids, arylsulfonic acid compounds such as 1, 4-benzodioxan disulfonic acid compound described in international publication No. 2005/000832, naphthalene or anthracene sulfonic acid compound described in international publication No. 2006/025342, dinonylnaphthalenesulfonic acid compound described in japanese patent application laid-open No. 2005-108828; organic oxidants such as 7, 7, 8, 8-Tetracyanoquinodimethane (TCNQ), 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ), and iodine, and inorganic oxidants such as heteropoly acids described in International publication No. 2010/058777, including phosphomolybdic acid, phosphotungstic acid, and phosphotungstomolybdic acid, may be used in combination.

Of these, preferred are aryl sulfonic acid compounds, and preferred are aryl sulfonic acid compounds represented by the formula (H1) or (H2). In view of solubility in an organic solvent, the molecular weight of the arylsulfonic acid compound used as a dopant substance is preferably 3000 or less, and more preferably 2500 or less.

[ solution 47]

A¹Represents O or S, preferably O.

A²Represents a naphthalene ring or an anthracene ring, preferably a naphthalene ring.

A³Represents a 2-4 valent perfluorobiphenyl group, p represents A¹And A³The number of binding of (A) is an integer satisfying 2. ltoreq. p.ltoreq.4³Is perfluorobiphenylene, preferably perfluorobiphenyl-4, 4' -diyl and p is 2.

q represents the same as A²The number of the sulfonic acid groups bonded is an integer satisfying 1. ltoreq. q.ltoreq.4, and 2 is most preferable.

A⁴～A⁸Independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms or a haloalkenyl group having 2 to 20 carbon atoms, A⁴～A⁸At least 3 of which are halogen atoms.

Examples of the haloalkyl group having 1 to 20 carbon atoms include a trifluoromethyl group, a 2, 2, 2-trifluoroethyl group, a1, 1,2, 2, 2-pentafluoroethyl group, a 3,3, 3-trifluoropropyl group, a 2, 2, 3,3, 3-pentafluoropropyl group, a1, 1,2, 2, 3,3, 3-heptafluoropropyl group, a 4,4, 4-trifluorobutyl group, a 3,3, 4,4, 4-pentafluorobutyl group, a 2, 2, 3,3, 4,4, 4-heptafluorobutyl group, and a1, 1,2, 2, 3,3, 4,4, 4-nonafluorobutyl group.

Examples of the haloalkenyl group having 2 to 20 carbon atoms include perfluorovinyl group, perfluoropropenyl group (perfluoroallyl group), perfluorobutenyl group, and the like.

Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom, and a fluorine atom is preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include the same ones as described above.

Of these, A is preferred⁴～A⁸Is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkenyl group having 2 to 10 carbon atoms, and A⁴～A⁸At least 3 of them are fluorine atoms, more preferably hydrogen atoms, fluorine atoms, cyano groups, C1-5 alkyl groups, C1-5 fluoroalkyl groups, or C2-5 fluoroalkenyl groups, and A⁴～A⁸At least 3 of them are fluorine atoms, more preferably hydrogen atoms, fluorine atoms, cyano groups, perfluoroalkyl groups having 1 to 5 carbon atoms, or perfluoroalkenyl groups having 1 to 5 carbon atoms, andA⁴、A⁵and A⁸Is a fluorine atom.

The perfluoroalkyl group is a group in which all of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, and the perfluoroalkenyl group is a group in which all of the hydrogen atoms of the alkenyl group are replaced with fluorine atoms.

r represents the number of sulfonic acid groups bonded to the naphthalene ring, and is an integer satisfying 1. ltoreq. r.ltoreq.4, preferably 2 to 4, and most preferably 2.

Specific examples of preferred arylsulfonic acid compounds are shown below, but the aryl sulfonic acid compounds are not limited thereto.

[ solution 48]

The organic solvent is not particularly limited as long as it can dissolve or disperse the charge transporting substance and the dopant substance, and examples thereof include benzene, toluene, o-xylene, m-xylene, p-xylene, N-methylformamide, N-dimethylformamide, N-diethylformamide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, cyclohexanol, ethylene glycol, 1, 3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1, 3-butanediol, 2, 3-butanediol, 1, 4-butanediol, propylene glycol, hexylene glycol, tetrahydrofurfuryl alcohol, butyl cellosolve, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl carbitol, diacetone alcohol, gamma-butyrolactone, ethyl lactate, n-hexyl acetate, and the like, and these may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The charge transporting composition of the present invention has a viscosity of usually 1 to 50 mPas at 25 ℃ and a surface tension of usually 20 to 50mN/m at 25 ℃.

The viscosity and surface tension of the charge transporting composition of the present invention can be adjusted by changing the kind of the organic solvent used, the ratio thereof, the solid content concentration, and the like, in consideration of various factors such as the coating method used and the desired film thickness.

The solid content concentration of the charge transporting composition of the present invention is suitably set in consideration of the viscosity, surface tension, and the like of the composition, the thickness of the produced film, and the like, and is usually about 0.1 to 15.0 mass%, and is preferably 10.0 mass% or less, more preferably 8.0 mass% or less, and further preferably 5 mass% or less from the viewpoint of suppressing aggregation of the charge transporting substance in the composition, and the like.

The solid content in the solid content concentration referred to herein means a component other than the solvent contained in the charge transporting composition of the present invention.

The charge transporting composition of the present invention can be produced by mixing the charge transporting substance of the present invention, an organic solvent, and a dopant substance used as needed. The mixing order is not particularly limited.

In the preparation of the composition, the composition can be appropriately heated within a range in which the components are not decomposed or deteriorated.

In the present invention, from the viewpoint of obtaining a film having a higher flatness with good reproducibility, it is preferable to dissolve a charge transporting substance or the like in an organic solvent and then perform filtration using a submicron filter or the like.

The charge-transporting thin film of the present invention can be formed on a substrate by applying the charge-transporting composition described above on the substrate and baking the composition.

The coating method of the composition is not particularly limited, and a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an ink jet method, a spray coating method, a slit coating method, and the like can be mentioned.

When the charge transporting composition of the present invention is used, the firing atmosphere is not particularly limited, and a thin film having a uniform film formation surface and a high charge transport property can be obtained not only in an atmospheric atmosphere (under air) but also in an inert gas such as nitrogen or a vacuum.

The firing conditions are not particularly limited, and firing by heating using a hot plate, for example. In general, the firing temperature is suitably determined in the range of 100 to 260 ℃ and the firing time is suitably determined in the range of 1 minute to 1 hour, taking into consideration desired charge transport properties and the like. Further, the firing may be performed in multiple stages at 2 or more different temperatures, if necessary.

The thickness of the charge transporting thin film is not particularly limited, and is preferably 5 to 300nm when used as a functional layer of an organic EL element. As a method for changing the film thickness, there are methods of changing the concentration of solid components in the charge transporting composition, changing the amount of liquid at the time of application, and the like.

The fluorinated aniline derivative or the polymer of the present invention contains a fluorine atom, and therefore can be used as an additive to be added to a charge-transporting composition containing another charge-transporting substance, for the main purposes of improving coating properties, improving transparency of the obtained film, and adjusting film properties such as wettability of the film surface.

[6] Organic EL element

The organic EL device of the present invention has a pair of electrodes, and the charge transporting thin film of the present invention is provided between the electrodes.

Typical configurations of the organic EL element include the following (a) to (f), but are not limited thereto. In the following configuration, an electron blocking layer or the like may be provided between the light-emitting layer and the anode, and a hole (hole) blocking layer or the like may be provided between the light-emitting layer and the cathode, as necessary. The hole injection layer, the hole transport layer, or the hole injection transport layer may have a function as an electron blocking layer or the like, and the electron injection layer, the electron transport layer, or the electron injection transport layer may have a function as a hole (hole) blocking layer or the like.

(a) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

(b) Anode/hole injection layer/hole transport layer/light emitting layer/electron injection transport layer/cathode

(c) Anode/hole injection transport layer/luminescent layer/electron transport layer/electron injection layer/cathode

(d) Anode/hole injection transport layer/light emitting layer/electron injection transport layer/cathode

(e) Anode/hole injection layer/hole transport layer/light emitting layer/cathode

(f) Anode/hole injection transport layer/light emitting layer/cathode

The "hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between the light-emitting layer and the anode, and have a function of transporting holes from the anode to the light-emitting layer, and are "hole injection transport layer" when only 1 layer of a hole-transporting material is provided between the light-emitting layer and the anode, and are "hole injection layer" when 2 or more layers of a hole-transporting material are provided between the light-emitting layer and the anode, the layer close to the anode is the "hole injection layer", and the other layers are the "hole transport layers". In particular, a thin film excellent in hole accepting property from the anode and hole injecting property into the hole transporting (light emitting) layer is used as the hole injecting (transporting) layer.

The "electron injection layer", "electron transport layer" and "electron injection transport layer" are layers formed between the light-emitting layer and the cathode, and have a function of transporting electrons from the cathode to the light-emitting layer, and are the "electron injection transport layer" when only 1 layer of an electron-transporting material is provided between the light-emitting layer and the cathode, and are the "electron injection layer" when 2 or more layers of an electron-transporting material are provided between the light-emitting layer and the cathode, the layer close to the cathode is the "electron injection layer", and the other layers are the "electron transport layers".

The "light-emitting layer" is an organic layer having a light-emitting function, and in the case of using a dopant system, includes a host material and a dopant material. In this case, the host material mainly has a function of promoting recombination of electrons and holes and confining excitons in the light-emitting layer, and the dopant material has a function of efficiently emitting excitons obtained by the recombination. In the case of a phosphorescent element, the host material mainly has a function of confining excitons generated from the dopant within the light emitting layer.

The charge-transporting thin film of the present invention can be preferably used as an organic functional film provided between an anode and a light-emitting layer in an organic EL device, can be more preferably used as a hole injection layer, a hole transport layer, a hole injection transport layer, and a further preferably used as a hole injection layer.

Examples of the materials and methods for producing the organic EL element using the charge transporting composition of the present invention include, but are not limited to, the following materials and methods.

An example of a method for manufacturing an OLED element having a hole injection layer composed of a thin film obtained from the charge transporting composition of the present invention is as follows. Furthermore, it is preferable that the electrode is previously cleaned with alcohol, pure water, or the like within a range that does not adversely affect the electrode; surface treatment such as UV ozone treatment, oxygen-plasma treatment, or the like is employed.

On the anode substrate, a hole injection layer was formed using the charge transporting composition by the method described above. The organic electroluminescent material is introduced into a vacuum evaporation device, and a hole transport layer, a luminescent layer, an electron transport layer/hole blocking layer, an electron injection layer and cathode metal are evaporated in sequence. Alternatively, in this method, instead of forming the hole transport layer and the light-emitting layer by vapor deposition, a composition for forming a hole transport layer containing a hole transport polymer and a composition for forming a light-emitting layer containing a light-emitting polymer are used, and these layers are formed by a wet method. Further, an electron blocking layer may be provided between the light-emitting layer and the hole transporting layer as necessary.

Examples of the anode material include a transparent electrode typified by Indium Tin Oxide (ITO) and Indium Zinc Oxide (IZO), a metal anode typified by aluminum, an alloy thereof, and the like, and a flattened anode material is preferable. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used.

Examples of the other metal constituting the metal anode include gold, silver, copper, indium, and alloys thereof, but are not limited thereto.

Examples of the material for forming the hole transport layer include triarylamines such as (triphenylamine) dimer derivatives, [ (triphenylamine) dimer ] spiro dimer, N '-bis (naphthalene-1-yl) -N, N' -bis (phenyl) -benzidine (. alpha. -NPD), 4 '-tris [ 3-methylphenyl (phenyl) amino ] triphenylamine (m-MTDATA), and 4,4' -tris [ 1-naphthyl (phenyl) amino ] triphenylamine (1-TNATA), and 5, 5 '-bis- {4- [ bis (4-methylphenyl) amino ] phenyl } -2, 2': and oligophenes such as 5 ', 2' -terthiophene (BMA-3T).

Examples of the material for forming the light-emitting layer include low-molecular-weight light-emitting materials such as metal complexes of 8-hydroxyquinoline and the like, metal complexes of 10-hydroxybenzo [ h ] quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, metal complexes of (2-hydroxyphenyl) benzothiazole, silole derivatives and the like; and a system in which a light-emitting material and an electron-transporting material are mixed in a polymer compound such as poly (p-phenylene vinylene), poly [ 2-methoxy-5- (2-ethylhexyloxy) -1, 4-phenylene vinylene ], poly (3-alkylthiophene) or polyvinylcarbazole.

In addition, when the light-emitting layer is formed by vapor deposition, the light-emitting layer may be co-deposited with a light-emitting dopant, and examples of the light-emitting dopant include tris (2-phenylpyridine) iridium (III) (ir (ppy)₃) And metal complexes, tetracene derivatives such as rubrene, quinacridone derivatives, fused polycyclic aromatic rings such as perylene, and the like.

Examples of the material for forming the electron transport layer/hole blocking layer include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives.

As a material for forming the electron injection layer, lithium oxide (Li) can be mentioned₂O), magnesium oxide (MgO), aluminum oxide (Al)₂O₃) And metal fluorides such as lithium fluoride (LiF) and sodium fluoride (NaF), but the metal fluorides are not limited thereto.

Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.

Examples of the material for forming the electron blocking layer include tris (phenylpyrazole) iridium and the like.

Examples of the hole-transporting polymer include poly [ (9, 9-dihexylfluorene-2, 7-diyl) -co- (N, N '-bis { p-butylphenyl } -1, 4-diaminophenylene) ], poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co- (N, N' -bis { p-butylphenyl } -1,1 '-biphenylene-4, 4-diamine) ], poly [ (9, 9-bis { 1' -penten-5 '-yl } fluorene-2, 7-diyl) -co- (N, N' -bis { p-butylphenyl } -1, 4-diaminophenylene) ], poly [ N ] terminated with polysilsesquioxane, n ' -bis (4-butylphenyl) -N, N ' -bis (phenyl) -benzidine ], poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co- (4, 4' - (N- (p-butylphenyl)) diphenylamine) ], and the like.

Examples of the light-emitting polymer include polyfluorene derivatives such as poly (9, 9-dialkylfluorene) (PDAF), polyphenylene vinylene derivatives such as poly (2-methoxy-5- (2' -ethylhexyloxy) -1, 4-phenylene vinylene) (MEH-PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

The organic EL element of the present invention can be sealed with a water-capturing agent or the like as needed in accordance with a conventional method in order to prevent deterioration of the characteristics.

Examples

The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[ device ]

The physical properties of the sample were measured under the following conditions using the following apparatus.

(1) Liquid chromatography (tracing of the reaction)

The device comprises the following steps: (Zu) Shimadzu manufacturing Ltd

UV-VIS detector: SPD-20A

Column oven: CTO-20A

A degassing unit: DGU-20A

A liquid feeding unit: LC-20AB

An automatic sampler: SIL-20A

Column: poroshell 120 EC-C18(2.7 μm, 3.0X 50mm, Agilent)

Column temperature: 40 deg.C

Solvent: acetonitrile/water acetonitrile concentration: 40% (0-0.01 min) → 40% -100% (0.01-5 min) → 100% (5-15 min) (vol/vol)

A detector: UV (ultraviolet) light

(2) Gel permeation chromatography (molecular weight determination of polymers)

The device comprises the following steps: (Zu) Shimadzu manufacturing Ltd

UV-VIS detector: SPD-20A

Differential refractometer detector: RID-20A

Column oven: CTO-20A

A degassing unit: DGU-20A

A liquid feeding unit: LC-20AD

An automatic sampler: SIL-20A

Column: shodex KF-G + KF-804L

Column temperature: 40 deg.C

Solvent: tetrahydrofuran (THF)

A detector: UV (ultraviolet) light

(3) Coating of the composition: ミカサ Kabushiki Kaisha spin coater MS-A100

(4) And (3) manufacturing an element: multifunctional evaporation device system C-E2L1G1-N manufactured by Changzhou industry

(5) Measurement of current density of element: (there are) テック & ワールド manufacturing I-V-L measurement system

(6) Glass transition temperature (Tg) measuring device: diamond DSC manufactured by Perkin elmer

The measurement conditions were as follows: under nitrogen atmosphere

Temperature rise rate: 5 ℃/min (40-300 ℃ C.)

(7) 5% weight loss temperature (Td 5%) determination

The device comprises the following steps: TG8120 manufactured by Rigaku

The measurement conditions were as follows: under the air atmosphere

Temperature rise rate: 10 ℃/min (40-500 ℃ C.)

(8) Automatic column chromatography (target fractionation): showa サイエンティフィック K.K. Purif-espoir2

(9) NMR: avance III 500MHz manufactured by Bruker

Internal standard

¹⁹F-NMR chemical shift correction

Benzotrifluoride ═ 64ppm

¹³C-NMR chemical shift correction

Acetone-d 6-206.68 ppm

Chloroform-d 1-77.23 ppm

N, N-dimethylformamide-d 7 ═ 163.15ppm

Tetrahydrofuran-d 8 ═ 67.57ppm

[ reagent ]

The reagents used in the following examples and comparative examples are as follows.

Pd(PPh₃)₄[ Tokyo chemical industry Co., Ltd.)]

Pd(DBA)₂[ Tokyo chemical industry Co., Ltd.)]

Pd(dppf)Cl₂[ Tokyo chemical industry Co., Ltd.)]

t-BuONa [ キシダ chemical products ]

BINAP (manufactured by Tokyo chemical industry Co., Ltd.)

Cesium carbonate [ pure chemical products ]

Magnesium sulfate [ キシダ chemical products ]

Potassium acetate [ manufactured by pure chemical Co. ]

Lithium Hexamethyldisilazide (LHMDS)1.3mol/L tetrahydrofuran solution [ manufactured by Tokyo chemical industry Co., Ltd ]

Hexamethyldisilazane lithium amide (LHMDS)1mol/L toluene solution [ manufactured by Aldrich Co ]

RuPhos (manufactured by Aldrich Co.)

t-BuXPhos [ manufactured by Aldrich Co. ]

SPhos [ manufactured by Aldrich Co. ]

t-BuMePhos [ manufactured by Aldrich Co. ]

JhonPhos [ manufactured by Aldrich Co. ]

CyJhonPhos [ manufactured by Aldrich ] company

N, N-dimethylformamide [ manufactured by pure chemical Co., Ltd ]

Ethyl acetate [ manufactured by Tokyo chemical industry Co., Ltd. ] or pure chemical industry Co., Ltd. ]

Toluene [ manufactured by pure chemical Co., Ltd. ] or manufactured by Kanto chemical Co., Ltd. ]

Dioxane [ manufactured by KANTO CHEMICAL Co., Ltd ]

Hexane [ pure chemical (manufactured) ]

Tetrahydrofuran [ pure chemical (strain) manufacture ]

Tetrahydrofurfuryl alcohol [ manufactured by KANTONG CHEMICAL Co., Ltd ]

Pentafluoroaniline [ manufactured by Tokyo chemical industry Co. ]

Fluorobenzene [ manufactured by Tokyo chemical industry Co. ]

Chlorobenzene [ manufactured by Tokyo chemical industry Co., Ltd ]

Bromobenzene [ manufactured by Tokyo chemical industry Co. ]

Iodobenzene [ manufactured by Tokyo chemical industry Co., Ltd ]

Bromopentafluorobenzene [ manufactured by Tokyo chemical industry Co. ]

2-fluoroaniline [ manufactured by Tokyo chemical industry Co., Ltd ]

4-Bromoanisole (manufactured by Tokyo chemical industry Co., Ltd.)

4,4' -Diaminooctafluorobiphenyl [ manufactured by Tokyo chemical industry Co., Ltd ]

1-bromo-4-tert-butylbenzene [ manufactured by Tokyo chemical industry Co., Ltd ]

1-bromonaphthalene [ pure chemical (manufactured by Kabushiki Kaisha) ]

2-bromonaphthalene [ manufactured by Tokyo chemical industry Co. ]

4-Bromotriphenylamine [ manufactured by Tokyo chemical industry Co., Ltd ]

4-iodotriphenylamine [ manufactured by Tokyo chemical industry Co., Ltd ]

4-bromo-4' - (diphenylamino) biphenyl [ Fuji film and Wako Junyaku Co. ]

2-bromo-9, 9' -spirobi [ 9H-fluorene ] [ manufactured by Tokyo chemical industry Co., Ltd ]

4,4' -dibromo-biphenyl [ manufactured by Tokyo chemical industry Co., Ltd ]

1, 4-dibromobenzene [ manufactured by Tokyo chemical industry Co., Ltd ]

3, 6-dibromo-9-phenylcarbazole [ manufactured by Fuji film and Wako pure chemical industries, Ltd ]

2, 7-dibromo-9, 9-dimethylfluorene [ manufactured by Tokyo chemical industry Co., Ltd ]

4-Fluorobromobenzene [ manufactured by Tokyo chemical industry Co., Ltd ]

[1] Synthesis of fluorinated secondary aromatic amine compounds

(1) Reaction of pentafluoroaniline with 4-bromoanisole

[ solution 49]

Comparative examples 1 to 1

Pd (PPh) was measured in a 30mL reaction flask equipped with a reflux column₃)₄0.05mmol (57.8mg), t-BuONa1.2mmol (115.3mg), and 1.2mmol (219.7mg) of pentafluoroaniline were added to the system, and the nitrogen was replaced. 4mL of dioxane and 1mmol (187.0mg) of 4-bromoanisole were added thereto, and after stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃ C.), and peaks attributable to the raw materials were confirmed but peaks attributable to the target substances were not confirmed in liquid chromatography using a trace amount of the solution obtained from the flask.

Comparative examples 1 and 2

Pd (PPh) was measured in a 30mL reaction flask equipped with a reflux column₃)₄0.05mmol (57.8mg), (+ -) -BINAP0.075mmol (46.7mg), cesium carbonate 1.2mmol (391.0mg), and pentafluoroaniline 1.2mmol (219.7mg) were added to the system, and nitrogen substitution was performed. 4mL of dioxane and 1mmol (187.0mg) of 4-bromoanisole were added thereto, and after stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃ C.), and peaks attributable to the raw materials were confirmed but peaks attributable to the target substances were not confirmed in liquid chromatography using a trace amount of the solution obtained from the flask.

Comparative examples 1 to 3

Pd (PPh) was measured in a 30mL reaction flask equipped with a reflux column₃)₄0.05mmol (57.8mg), (+ -) -BINAP0.075mmol (46.7mg), and 1.2mmol (219.7mg) of pentafluoroaniline were added to the system, and nitrogen substitution was performed. 4mL of dioxane and 1mmol (187.0mg) of 4-bromoanisole were added thereto, and LHMDS1.3mol/L tetrahydrofuran was further added0.923mL (equivalent to LHMDS1.2mmol) of the pyran solution was stirred at room temperature for 5 minutes, and then stirred by heating at 110 ℃ for 5 hours (inner temperature: 92 ℃) in a bath, peaks attributable to the raw materials were observed in a liquid chromatogram using a trace amount of the solution obtained from the flask, but peaks attributable to the target product were not observed.

Comparative examples 1 to 4

The operation was carried out in the same manner as in comparative examples 1 to 3 except that ruphos0.075mmol (35.0mg) represented by the following formula (L2) was used instead of (±) BINAP, and peaks attributable to the raw material could be confirmed but peaks attributable to the target substance could not be confirmed in liquid chromatography using a trace amount of the solution obtained from the flask.

[ solution 50]

(wherein i-Pr represents an isopropyl group, and Cy represents a cyclohexyl group.)

Comparative examples 1 to 5

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.05mmol (28.8mg) and 1.2mmol (219.7mg) of pentafluoroaniline were added to the system, and the mixture was replaced with nitrogen. To this mixture, 4mL of dioxane and 1mmol (187.0mg) of 4-bromoanisole were added, and 0.923mL (equivalent to lhmds1.2mmol) of lhmds1.3mol/L tetrahydrofuran solution was further added, and after stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 ℃ for 5 hours (inner temperature 92 ℃), and peaks attributable to the raw material could be confirmed but peaks attributable to the target material could not be confirmed in liquid chromatography using a trace amount of the solution obtained from the flask.

Comparative examples 1 to 6

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.05mmol (28.8mg), (+ -) -BINAP0.075mmol (46.7mg), pentafluoroaniline 1.2mmol (219.7mg), and cesium carbonate 1.2mmol (391.0mg), and the system was subjected to nitrogen substitution. 4mL of dioxane and 1mmol (187.0mg) of 4-bromoanisole were added thereto, and after stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 ℃ for 5 hours (inner temperature 92 ℃),in liquid chromatography using a trace amount of solution obtained from the flask, peaks attributable to the raw material could be confirmed, but peaks attributable to the target substance could not be confirmed.

Comparative examples 1 to 7

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.05mmol (28.8mg), (+ -) -BINAP0.075mmol (46.7mg), and 1.2mmol (219.7mg) of pentafluoroaniline were added to the system, and nitrogen substitution was performed. To this mixture, 4mL of dioxane and 1mmol (187.0mg) of 4-bromoanisole were added, and 0.923mL (equivalent to lhmds1.2mmol) of lhmds1.3mol/L tetrahydrofuran solution was further added, and after stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 ℃ for 5 hours (inner temperature 92 ℃), and peaks attributable to the raw material could be confirmed but peaks attributable to the target material could not be confirmed in liquid chromatography using a trace amount of the solution obtained from the flask.

[ example 1-1]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.05mmol (28.8mg), RuPhos0.075mmol (35.0mg), cesium carbonate 1.2mmol (391.0mg), and pentafluoroaniline 1.2mmol (219.7mg), and the system was subjected to nitrogen substitution. To this mixture were added 4mL of dioxane and 1mmol (187.0mg) of 4-bromoanisole, followed by stirring at room temperature for 5 minutes, followed by addition of 0.923mL of lhmds1.3mol/L tetrahydrofuran solution (lhmds1.2mmol), stirring at room temperature for 5 minutes, and then stirring at 110 ℃ for 5 hours (internal temperature 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no distinct peak corresponding to the by-product was confirmed.

After the reaction mixture was cooled to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50mL of a saturated aqueous ammonium chloride solution and 30mL of ethyl acetate, extraction was performed to leave an organic layer in the separatory funnel, and an aqueous layer was collected. 50mL of a saturated saline solution was put into a separatory funnel, and the remaining organic layer was washed and the aqueous layer and the organic layer were collected. Then, all the collected aqueous layers were combined, placed in a separatory funnel, and 20mL of ethyl acetate was added thereto to conduct extraction, and the organic layers were collected, and all the collected organic layers were combined and dried over magnesium sulfate.

Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The obtained residue was dissolved in 3mL of toluene, and the obtained solution was subjected to column chromatography (elution solvent: hexane/ethyl acetate 100/0 → 97/3) to collect fractions containing the target substance.

Finally, the solvent was removed from the fractions collected at 80 ℃ under reduced pressure to obtain 67.2mg of the objective compound (yield 26%).

¹H NMR(500.13MHz,CDCl₃):δ＝3.76(s,3H),5.14(brs,1H),6.72-6.75(m,6H),6.8(d,J＝9.0Hz,2H)

¹³C NMR(125.77MHz,CDCl₃):δ＝55.8,114.7,119.5,120.1,135.4,136.3,138.5,140.6,155.9

¹⁹F NMR(470.53MHz,CDCl₃) δ -167.6(t, J-21.7 Hz,1F), -164.5(td, J-21.7, 5.2Hz,2F), -153.3(brd, 2F); IR (pure)

ν～＝3314(w),3063(w),2968(w),1694(s),1670(m),1653(m),1609(m),1590(m),1503(s),1460(m),1440(s),1414(m),1295(m),1196(m),1176(m),1138(w),1119(m),1106(m),1073(w),1022(m),1008(m),982(s),905(m),845(m),765(s),753(m),735(m),697(m)

HRMS(ESI):C₁₃H₈F₅NO(M+H)⁺289.0526, found 290.0589.

[ examples 1-2]

The reaction and the post-treatment were carried out in the same manner as in example 1-1 except that t-BuONa1.2mmol (115.3mg) was used instead of cesium carbonate to obtain 286.1mg of the objective compound (yield > 99%).

[ examples 1 to 3]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.05mmol (28.8mg), RuPhos0.075mmol (35.0mg), and 1.2mmol (219.7mg) of pentafluoroaniline were added to the system, and nitrogen was substituted. To this was added 4mL of dioxane and 1mmol (187.0mg) of 4-bromoanisole, and the mixture was stirred at room temperature for 5 minutes, followed by addition of LHMDS1.0.923mL (equivalent to LHMDS1.2mmol) of a 3mol/L tetrahydrofuran solution was stirred at room temperature for 5 minutes, and then the mixture was heated and stirred in a bath at 110 ℃ for 3 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no distinct peak corresponding to the by-product was confirmed.

Finally, the solvent was removed from the fractions collected at 80 ℃ under reduced pressure to obtain 287.3mg of the target product (> 99% yield).

[ examples 1 to 4]

The reaction and the post-treatment were carried out in the same manner as in example 1-3 except that RuPhos0.2mmol (93.3mg) was used for a reaction time of 5 hours, to obtain 286.0mg of the objective compound (yield > 99%).

[ examples 1 to 5]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 3 except that t-BuXPhos0.075mmol (31.8mg) represented by the following formula (L4) was used instead of RuPhos for a reaction time of 5 hours to obtain 243.9mg (yield 84%) of the objective compound.

[ solution 51]

(wherein i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group.)

[ examples 1 to 6]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 3 except that SPhos0.075mmol (30.8mg) represented by the following formula (L1) was used instead of RuPhos for a reaction time of 5 hours to obtain 246.0mg (yield 85%) of the objective compound.

[ solution 52]

(wherein Me represents a methyl group and Cy represents a cyclohexyl group.)

[ examples 1 to 7]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 3 except that t-BuMePhos0.075mmol (23.4mg) represented by the following formula (L5) was used instead of RuPhos for a reaction time of 5 hours to obtain 246.3mg of the objective compound (yield: 85%).

[ Hua 53]

(wherein Me represents a methyl group and t-Bu represents a tert-butyl group.)

[ examples 1 to 8]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 3 except that Jhon phos0.075mmol (22.4mg) represented by the following formula (L6) was used instead of Ruphos for a reaction time of 5 hours to obtain 268.2mg of the objective compound (yield 95%).

[ solution 54]

(wherein t-Bu represents a tert-butyl group.)

[ examples 1 to 9]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 3 except that CyJhonPhos0.075mmol (26.3mg) represented by the following formula (L7) was used instead of RuPhos for a reaction time of 5 hours to obtain 208.9mg of the objective compound (yield 73%).

[ solution 55]

(wherein Cy represents cyclohexyl.)

A summary of examples 1-1 to 9 and comparative examples 1-1 to 1-7 is shown in Table 1.

[ Table 1]

Examples 1-4 RuPhos0.2mmol

(2) Reaction of pentafluoroaniline with halogenated aryl groups

[ solution 56]

Comparative examples 1 to 8

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.05mmol (28.8mg), RuPhos0.075mmol (35.0mg), and 1.2mmol (219.7mg) of pentafluoroaniline were added to the system, and nitrogen was substituted. 4mL of dioxane and 1mmol (96.1mg) of fluorobenzene were added thereto, and the mixture was stirred at room temperature for 5 minutes, followed by addition of 0.923mL (equivalent to 1.2mmol) of LHMDS1.3mol/L tetrahydrofuran solution, and after stirring at room temperature for 5 minutes, the mixture was stirred at 110 ℃ in a bath for 5 hours (inner temperature: 92 ℃). In addition, a reaction was followed by liquid chromatography using a trace amount of a solution obtained from the flask in the middle, and a large number of distinct peaks that could not be assigned to the target substance were confirmed in addition to peaks that could be assigned to the raw material.

Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The obtained residue was dissolved in 3mL of toluene, and the obtained solution was subjected to column chromatography (elution solvent: hexane/ethyl acetate 100/0 → 97/3) to separate a fraction other than a fraction mainly containing the raw material.

Finally, the solvent was removed from the fraction fractionated at 80 ℃ under reduced pressure to obtain a solid. However, in the solid obtained¹In the H-NMR spectrum, a large number of peaks were found which could not be ascribed to the starting material or the target. This mixture was a mixture containing a plurality of by-products, and it was judged that it was difficult to separate the target substance therefrom, and no purification other than this was attempted.

[ examples 1 to 10]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.05mmol (28.8mg), RuPhos0.075mmol (35.0mg), and 1.2mmol (219.7mg) of pentafluoroaniline were added to the system, and nitrogen was substituted. 4mL of dioxane and 1mmol (112.6mg) of chlorobenzene were added thereto, and the mixture was stirred at room temperature for 5 minutes, followed by addition of 0.923mL (equivalent to 1.2mmol of LHMDS1.3mol/L tetrahydrofuran solution) of LHMDS1.3mol/L tetrahydrofuran solution, and after stirring at room temperature for 5 minutes, the mixture was stirred at 110 ℃ for 3 hours (inner temperature: 92 ℃ C.). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Finally, the solvent was removed from the fractions collected at 80 ℃ under reduced pressure to obtain 195.7mg of the objective compound (yield 81%).

[ examples 1 to 11]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 10 except that 1mmol (157.0mg) of bromobenzene was used instead of chlorobenzene for a reaction time of 5 hours to obtain 256.6mg of the objective compound (yield > 99%).

[ examples 1 to 12]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 10 except that toluene was used instead of dioxane and 1.2mL (equivalent to LHMDS1.2mmol) of LHMDS1mol/L toluene solution was used instead of LHMDS1.3mol/L tetrahydrofuran solution to adjust the reaction time to 5 hours, thereby obtaining 243.5mg (yield 94%) of the objective compound.

[ examples 1 to 13]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 10 except that 1mmol (204.0mg) of iodobenzene was used instead of chlorobenzene to obtain 257.4mg of the objective compound (yield > 99%).

[ examples 1 to 14]

[ solution 57]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.05mmol (28.8mg), RuPhos0.075mmol (35.0mg), pentafluoroaniline 1.2mmol (219.7mg), and 4-fluorobromobenzene 1mmol (175.0mg), and the system was subjected to nitrogen substitution. 4mL of dioxane was added thereto, and the mixture was stirred for 5 minutes, followed by 0.923mL (equivalent to LHMDS1.2mmol) of LHMDS1.3mol/L tetrahydrofuran solution, and after stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Finally, the solvent was removed from the fractions collected at 50 ℃ under reduced pressure to obtain 242.9mg of the objective compound (yield 88%).

¹H NMR(500.13MHz,CDCl₃):δ＝5.39(brs,1H),6.84(m,2h),7.00(brt,2H)

¹³C NMR(125.77MHz,CDCl₃):δ＝116.0,116.2,118.9,119.0,138.3,157.8,159.7

¹⁹F NMR(470.53MHz,CDCl₃):δ-165.6(brt,1F),-164.0(brdt,F),151.8(brd,2F),122.6(brs,1F)；

IR (pure) ν ═ 3425.6(m),1656.9(w),1504.5(s),1205.5(s),1153.4(m),1101.4(m),1008.8(s),997.9(s),827.5(s),748.4(m),717.5(m),702.1(m),669.3(m),636.5(m)

A summary of examples 1-10 to 1-14 and comparative examples 1-8 is shown in Table 2.

[ Table 2]

(3) Reaction of tetrafluoroaniline with 4-bromoanisole

[ solution 58]

[ examples 1 to 15]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.05mmol (28.8mg) and RuPhos0.075mmol (35.0mg), and the system was purged with nitrogen. To this was added 4mL of dioxane, 1.2mmol (133.3mg) of 2-fluoroaniline and 1mmol (187.0mg) of 4-bromoanisole, followed by stirring at room temperature for 5 minutes, followed by addition of 0.923mL (equivalent to 1.2mmol of lhmds) of lhmds1.3mol/L tetrahydrofuran solution, stirring at room temperature for 5 minutes, and then stirring at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Finally, the solvent was removed from the fractions collected at 80 ℃ under reduced pressure to obtain 217.6mg of the target product (yield 98%).

¹H NMR(500.13MHz,CDCl₃):δ＝3.84(s,3H),5.68(brs,1H),6.77-6.79(m,1H),6.93(d,J＝9.0Hz,2H),7.00(brt,1H),7.07-7.12(m,2H)；7.15(d,J＝9.0Hz,2H)

¹³C NMR(125.77MHz,CDCl₃):δ＝55.7,114.9,115.2,115.3,119.1,123.3,124.5,134.1,134.7,152.4,156.1

¹⁹F NMR(470.53MHz,CDCl₃) Delta-136.1 (brs); IR (pure)

ν～＝3382(m),3010(w),2938(w),2906(w),2838(w),1617(m),1585(w),1504(s),1477(m),1464(m),1455(m),1442(m),1332(m),1296(m),1288(m),1255(m),1233(s),1222(s),1180(s),1171(m),1109(m),1095(s),1029(s),1008(m),925(w),917(w),886(w),838(m),821(s),757(m),742(s),707(m),696(w)

HRMS(ESI):C₁₃H₁₂FNO(M+H)⁺217.0903, found 218.0963.

[ examples 1 to 16]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 15 except that 1.2mmol (133.3mg) of 3-fluoroaniline was used instead of 2-fluoroaniline, to obtain 210.6mg (yield: 97%) of the desired product.

¹H NMR(500.13MHz,CDCl₃):δ＝3.79(s,3H),5.57(brs,1H),6.47(ddd,J＝8.3,2.3,0.9Hz,1H),6.56(dt,J＝11.4,2.3Hz,1H),6.59(ddd,J＝8.3,2.2,0.9Hz,1H),6.87(d,J＝8.9,6.7Hz,2H),7.07(dd,J＝8.9,6.7Hz,2H),7.11(td,J＝8.3,6.7Hz,2H)

¹³C NMR(125.77MHz,CDCl₃):δ＝55.7,101.9,105.9,111.0,1145.0,123.6,130.6,134.8,147.7,156.2,164.2

¹⁹F NMR(470.53MHz,CDCl₃):δ＝-113.7(ms)

Nu- ═ 3361(m),3043(w),2966(w),2915(w),2839(w),1600(s),1584(m),1526(m),1506(s),1490(s),1465(m),1334(m),1290(m),1251(m),1181(w),1174(w),1168(w),1138(s),1109(s),1072(w),827(m),755(m),742(s)

HRMS(ESI):C₁₃H₁₂FNO(M+H)⁺217.0903, found 218.0969.

[ examples 1 to 17]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 15 except for using 1.2mmol (133.3mg) of 4-fluoroaniline instead of 2-fluoroaniline, to obtain 161.7mg of the objective compound (yield 74%).

¹H NMR(500.13MHz,CDCl₃):δ＝3.79(s,3H),5.36(brs,1H),6.84-7.25(m,8H)

¹³C NMR(125.77MHz,CDCl₃):δ＝55.8,115.0,116.0,118.0,121.4,136.8,141.4,155.3,157.4

¹⁹F NMR(470.45MHz,CDCl₃):δ＝-125.6(s)

IR (pure) v ~ 3392(w),3037(w),2955(w),2934(w),2834(w),1603(w),1590(w),1497(s),1464(m),1442(m),1316(m),1295(m),1245(m),1213(s),1179(m),1154(w),1109(w),1098(w),1034(m),818(s),773(m),696(w)

HRMS(ESI):C₁₃H₁₂FNO(M+H)⁺217.0903, found 218.0965.

[ examples 1 to 18]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 15 except for using 1.2mmol (154.9mg) of 2, 6-difluoroaniline instead of 2-fluoroaniline, to obtain 216.2mg (yield 92%) of the desired product.

¹H NMR(500.13MHz,CDCl₃):δ＝3.77(s,3H),5.37(brs,1H),6.81(brs,4H),6.91-6.93(m,3H)

¹³C NMR(125.77MHz,CDCl₃):δ＝55.8,112.0,114.6,118.8,121.0,121.9,137.1,154.9,156.1

¹⁹F NMR(470.45MHz,CDCl₃):δ＝-123.4(m)

IR (pure) v ═ 3411(w),2935(w),2835(w),1623(w),1598(w),1504(s),1456(m),1406(w),1294(m),1233(s),1179(m),1111(w),1060(w),1033(m),999(s),818(m),778(w),758(m),728(w),707(w),695(w)

HRMS(ESI):C₁₃H₁₁F₂NO(M+H)⁺235.0809, found 236.0867.

[ examples 1 to 19]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.05mmol (28.8mg), RuPhos0.075mmol (35.0mg), and 1.2mmol (176.5mg) of 2,4, 6-trifluoroaniline were added to the system, and the nitrogen was replaced. To this mixture was added 4mL of dioxane, 1mmol (187.0mg) of 4-bromoanisole, and after stirring for 5 minutes, 0.923mL (equivalent to LHMDS1.2mmol) of LHMDS1.3mol/L tetrahydrofuran solution was added, followed by heating and stirring at 110 ℃ for 4 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Finally, the solvent was removed from the fractions collected at 80 ℃ under reduced pressure to obtain 237.4mg of the objective compound (yield 91%).

¹H NMR(500.13MHz,CDCl₃):δ＝3.76(s,3H),5.14(brs,1H),6.72-6.75(m,3H),6.80(d,J＝9.0Hz,2H)

¹³C NMR(125.77MHz,CDCl₃):δ＝55.8,100.9,114.7,117.4,117.9,137.6,154.8,156.7,157.8

¹⁹F NMR(470.45MHz,CDCl₃):δ＝-119.8(brs),-116.9(brs)

IR (pure substance)' v ═ 3396(w),3083(w),2913(w),2837(w),1636(w),1608(w),1504(s),1442(m),1288(w),1235(s),1173(m),1116(s),1030(s),996(s),837(s),817(s)

HRMS(ESI):C₁₃H₁₀F₃NO(M+H)⁺253.0714, found 254.0772.

[ examples 1 to 20]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 19 except for using 1.2mmol (154.9mg) of 2, 3, 5, 6-tetrafluoroaniline instead of 2,4, 6-trifluoroaniline, to obtain 243.9mg (yield 90%) of the objective compound.

¹H NMR(500.13MHz,CDCl₃):δ＝3.79(s,3H),5.56(brs,1H),6.63(tt,J＝10.0,7.1Hz,1H),6.84(d,J＝8.9Hz,2H),6.92(brd,J＝8.9Hz,2H)

¹³C NMR(125.77MHz,CDCl₃):δ＝55.8,96.8,114.6,121.1,124.6,134.9,139.4,146.8,156.2

¹⁹F NMR(470.45MHz,CDCl₃) δ -154.00, -154.08(m,2F), -141.49, -141.57(m, 2F); IR (pure substance). nu- ═ 3398(m),3083(w),2927(w),2845(w),1646(m),1613(w),1526(s),1507(s),1497(s),1456(s),1409(m),1294(m),1261(m),1241(s),1172(s),1120(m),1112(m),1077(m),1031(m),949(s),820(s),804(m),769(m),726(m),709(m),691(m)

HRMS(ESI):C₁₃H₉F₄NO(M+H)⁺271.0620, found 272.0694.

A summary of the above examples 1-15 to 1-20 is shown in Table 3. The results of examples 1 to 3 are also shown.

[ Table 3]

[ examples 1 to 21]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.2mmol (115.0mg), RuPhos0.3mmol (140.0mg), and 2.5mmol (656.3mg) of 4,4' -diaminooctafluorobiphenyl were added to the system, and nitrogen substitution was performed. To this, 8mL of dioxane was added, 4.8mmol (753.6mg) of bromobenzene was further added, and after stirring for 5 minutes, 3.7mL of LHMDS1.3mol/L tetrahydrofuran solution (corresponding to LHMDS4.8mmol) was added, and the mixture was stirred while heating in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The obtained residue was dissolved in 3mL of toluene, and the obtained solution was subjected to column chromatography (elution solvent: hexane/ethyl acetate 100/0 → 90/10) to collect fractions containing the target substance.

Finally, the solvent was removed from the fractions collected at 80 ℃ under reduced pressure to obtain 0.88g of the objective compound (yield 92%).

¹H NMR(500.13MHz,CDCl₃):δ＝5.45(brs,1H),6.85(brd,2H),7.02(brt,1H),7.30(brt,2H)

¹³C NMR(125.77MHz,CDCl₃):δ＝116.7,122.2,129.5,142.3

¹⁹F NMR(470.53MHz,CDCl₃) δ -164.9(brt,1F), -164.1(dt, J-22.1, 5.8Hz,2F), -150.7(brd,2F), IR (purities) ν to 3408.2(m),1602.9(m),1521.8(S),1500.6(S),1483.3(S),1462.0(S),1421.54(S),1315.5(m),1292.31(m)

[ examples 1 to 22]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 21 except that 4.8mmol (1023.0mg) of 1-bromo-4-tert-butylbenzene was used instead of bromobenzene to obtain 1.07g of the objective compound (yield 91%).

¹H NMR (500.13MHz, acetone): δ 1.31(s,18H),7.03(d, J8.7 Hz,4H),7.36(d, J8.7 Hz,4H),7.78(brs,2H)

¹³C NMR (125.77MHz, acetone): delta-31.9, 34.8,98.5,118.9,125.9,126.6,140.4,141.2,146.0

¹⁹F NMR (470.45MHz, acetone): δ -152.67(brd, F), -143.45- (-143.1) (m,4F)

IR (pure substance) ~ 3406(w),3394(w),2966(w),2909(w),2869(w),1651(m),1610(m),1487(s),1449(m),1403(w),1394(w),1364(w),1291(w),1263(m),1243(m),1191(w),1125(w),1115(w),1082(m),996(m),976(s),829(m),821(s),728(m),723(s)

HRMS(ESI):C₃₂H₂₈F₈N₂(M+H)⁺592.2125, found 593.2170.

[ examples 1 to 23]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.2mmol (115.0mg), RuPhos0.3mmol (140.0mg), 4' -diamine2.5mmol (656.3mg) of octafluorobiphenyl and 4.8mmol (1388.2mg) of 4-bromo-4' -tert-butylbiphenyl were added, and the system was purged with nitrogen. 8mL of dioxane was added thereto, and after stirring for 5 minutes, 3.7mL of LHMDS1.3mol/L tetrahydrofuran solution (equivalent to LHMDS4.8mmol) was added thereto, and the mixture was stirred while heating in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Finally, the solvent was removed from the fractions collected at 80 ℃ under reduced pressure to obtain 892.6mg of the objective compound (yield 60%).

¹H NMR(500.13MHz,THF):δ＝1.38(s,18H),7.09(brd,4H),7.47(brd,4H),7.56(brt,8H),8.07(brs,2H)

¹³C NMR(125.77MHz,THF):δ＝31.9,34.8,98.5,118.9,125.9,126.6,140.4,141.2,146.0

¹⁹F NMR(470.45MHz,THF):δ＝-152.14(brd,F),-143.24,-143.29(m,4F)

Nu- ═ 3421(w),3030(w),2960(w),2902(w),2866(w),1651(m),1608(m),1510(s),1484(s),1457(s),1452(s),1394(w),1366(w),1359(w),1314(w),1293(w),1262(m),1238(w),1198(w),1184(w),1121(w),1114(w),1085(m),997(m),972(m),816(s),778(w),746(w),739(w),721(s),667(w)

HRMS(ESI):C₄₄H₃₆F₈N₂(M+H)⁺744.2751, found 745.2794.

[ examples 1 to 24]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 23 except that 4.8mmol (993.9mg) of 1-bromonaphthalene was used instead of 4-bromo-4' -tert-butylbiphenyl, to obtain 617.0mg (yield 68%) of the objective compound.

¹H NMR(500.13MHz,DMF):δ＝7.27(brd,2H),7.51(t,J＝7.8Hz,2H),7.59-7.64(m,4H),7.74(brd,2H),8.00-8.03(m,2H),8.47-8.50(m,2H),8.82(brs,2H)

¹³C NMR(125.77MHz,DMF):δ＝98.3,116.5,124.0,124.6,126.8,126.9,127.4,127.7,128.6,129126.9,127.4,127.7,128.6,129,135.6,141.4,146.1

¹⁹F NMR(470.45MHz,DMF):δ＝-153.18(brd,J＝13.9Hz,4F),-143.45-(-143.35)(m,4F)

IR (pure) v ~ 3396(w),3373(w),3063(w),1653(m),1595(m),1577(w),1522(m),1496(s),1489(s),1466(s),1430(m),1401(m),1391(m),1274(m),1267(m),1251(w),1241(w),1168(w),1154(w),1131(w),1106(m),1088(w),1075(w),1040(w),1017(w),986(s),955(s),794(s),772(s),727(s)

HRMS(ESI):C₃₂H₁₆F₈N₂(M+H)⁺580.1186, found 581.1249.

[ examples 1 to 25]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 23 except that 4.8mmol (993.9mg) of 2-bromonaphthalene was used instead of 4-bromo-4' -tert-butylbiphenyl, to obtain 770.2mg of the objective compound (yield 53%).

¹H NMR(500.13MHz,DMSO):δ＝7.23-7.35(m,6H),7.43(brt,2H),7.77(brd,2H),7.83(brt,4H),9.00(brs,2H)

¹³C NMR(125.77MHz,DMSO):δ＝98.2,111.9,119.9,124.2,124.4,126.9,127.0,128.0,129.0,129.4,134.3,140.3,140.9,144.9

¹⁹F NMR(470.45MHz,DMSO):δ＝-148.08(brd,4F),-140.33(brd,4F)

IR (pure) — nu 3412(m),3054(w),1651(m),1627(s),1602(m),1591(w),1506(s),1484(s),1456(s),1425(m),1290,1276,1264,1225(s),1183(m),1132(m),1091(s),999(s),967(s),846(s),823(s),746(s),732(s),708(m),641(m)

HRMS(ESI):C₃₂H₁₆F₈N₂(M+H)⁺580.1186, found 581.1249.

[ examples 1 to 26]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 23 except that 4.8mmol (1556.2mg) of 4-bromotriphenylamine was used instead of 4-bromo-4' -tert-butylbiphenyl, to obtain 1417.3mg (yield 87%) of the objective compound.

¹H NMR (500.13MHz, acetone): δ 6.98(t, J7.3, 4H),7.05(m,16H),7.26(dd, J8.6, 7.3Hz,8H),8.86(brs,2H)

¹³C NMR (125.77MHz, acetone): delta-99.1,120.9,123.7,124.7,126.2,127.3,130.7,139.4,141.7,143.8,146.5,149.6

¹⁹F NMR (470.45MHz, acetone): δ -152.72(brd, J-13.9 Hz,4F), -143.27(m,4F)

IR (pureness). nu-3394 (w),3023(w),1649(m),1586(m),1485(s),1410(m),1333(w),1319(w),1293(w),1273(m),1260(m),1235(m),1175(w),1156(w),1152(w),1132(w),1118(w),1112(w),1085(m),995(m),974(m),968(m),899(w),891(w),826(m),817(m),749(s),739(m),722(m),714(m),693(s)

HRMS(ESI):C₄₈H₃₀F₈N₄(M+H)⁺814.2343, found 814.2312.

[ examples 1 to 27]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 23 except that 4.8mmol (1781.9mg) of 4-iodotriphenylamine was used instead of 4-bromo-4' -tert-butylbiphenyl, to obtain 1101.3mg of the objective compound (yield 68%).

[ examples 1 to 28]

The reaction and the post-treatment were carried out in the same manner as in examples 1 to 23 except for using 4.8mmol (1921.5mg) of 4-bromo-4 '- (diphenylamino) biphenyl instead of 4-bromo-4' -tert-butylbiphenyl to obtain 1903.1mg (yield 99%) of the objective compound.

[ examples 1 to 29]

The reaction and the post-treatment were carried out in the same manner as in example 24 except for using 4.8mmol (1897.4mg) of 2-bromo-9, 9 '-spirobis [ 9H-fluorene ] instead of 4-bromo-4' -tert-butylbiphenyl to obtain 1.88g of the objective compound (yield 98%).

¹H NMR (500.13MHz, acetone): δ ═ 6.39(brs,2H),6.62(dd, J ═ 7.5,1.0Hz,2H),6.73(dd, J ═ 7.5,1.0Hz,4H),7.05-7.09(m,4H),7.16(td, J ═ 7.5,1.0Hz,4H),7.36(td, J ═ 7.5,1.0Hz,2H),7.40(td, J ═ 7.5,1.0Hz,4H),7.82(s,2H),7.89(brdd,4H)7.97(brd, J ═ 7.5,4H)

¹³C NMR (125.77MHz, acetone): delta-66.9, 99.0,114.6,118.0,120.5,121.1,121.5,124.5,124.8,125.1,127.9,128.6,128.88,136.9,141.2,142.7,142.8,142.9,145.8,149.4,149.9,151.0

¹⁹F NMR (470.45MHz, acetone): δ -152.3(brd,4F), -143.2(m,4F)

IR (pure substance) ~ 3391(w),3063(w),3042(w),3015(w),1653(m),1614(m),1488(s),1446(s),1346(w),1299(m),1290(m),1284(m),1267(m),1215(m),1167(w),1153(w),1120(m),1089(m),1078(m),979(m),967(m),851(w),821(m),750(s),735(s),725(s),717(s),636(m)

HRMS(ESI):C₆₂H₃₂F₈N₂(M+H)⁺956.2438, found 812.4212.

[ examples 1 to 30]

[ chemical 59]

Pd (dppf) Cl was measured in a100 mL reaction flask equipped with a reflux column₂0.45mmol (367.5mg), potassium acetate 45mmol (4416.3mg), 3-bromo-N-phenylCarbazole 15mmol (4833.2mg) and bis (pinacolato) diboron 11mmol (4190.0mg) were substituted with nitrogen in the system. To this was added 150mL of N, N-dimethylformamide, and after stirring for 5 minutes, the mixture was heated and stirred in a bath at 90 ℃ for 3 hours. Furthermore, the reaction was followed by a chromatography (TLC) method using a small amount of the reaction mixture obtained from the system.

After the reaction mixture was cooled to room temperature, the solvent was removed from the cooled reaction mixture under reduced pressure, the reaction mixture was concentrated, the concentrate was washed with 50mL of ion-exchanged water in a separatory funnel, 50mL of chloroform was added thereto, extraction was performed, and the organic layer was collected from the separatory funnel. Then, the recovered organic layer was dried over magnesium sulfate.

Magnesium sulfate was removed by filtration, the obtained filtrate was concentrated, and column chromatography (eluting solvent: hexane/ethyl acetate 100/0 → 96/4) was performed using the obtained concentrate to collect fractions containing the target substance.

Finally, the solvent was removed from the fractions collected under reduced pressure to obtain 4.21g of N-phenylcarbazol-3-yl-boronic acid pinacol ester (yield 76%).

¹H NMR(500.13MHz,CDCl₃):δ＝1.41(s、12H),7.29(ddd,J＝7.9,6.0,2.0Hz,1H),7.37(brd,J＝8.2Hz,1H),7.40(m,2H),7.48(t,J＝7.5Hz,1H),7.55(m,2H),7.61(m,2H),8.76(dd,J＝8.2,1.2Hz,2H),8.18(d,J＝7.6Hz,1H),8.64(s,1H)

[ solution 60]

Pd (PPh) was measured in a 50mL reaction flask equipped with a reflux column₃)₄0.09mmol (104.1mg), 9mmol (359.9mg) of sodium hydroxide, 3mmol (1107.8mg) of N-phenylcarbazol-3-yl-boronic acid pinacol ester, and 3.3mmol (1184.7mg) of 4-bromo-4' -iodobiphenyl were subjected to nitrogen substitution in the system. To this was added 13.5mL of a mixed solvent of tetrahydrofuran and water (2/1(v/v)), and after stirring for 5 minutes, the mixture was heated and stirred in a bath at 50 ℃ for 5 hours. Furthermore, chromatography (TL) using a reaction mixture obtained from the system in a very small amount was employedC) The method followed the reaction.

After the reaction mixture was cooled to room temperature, the solvent was removed from the cooled reaction mixture under reduced pressure, the reaction mixture was concentrated, the concentrate was washed with 50mL of ion-exchanged water in a separatory funnel, 50mL of tetrahydrofuran was added thereto, extraction was performed, and the organic layer was collected from the separatory funnel. Then, the recovered organic layer was dried over magnesium sulfate.

Finally, the solvent was removed from the fraction collected under reduced pressure to obtain 810mg of 4-bromo-4' - (N-phenylcarbazol-3-yl) -biphenyl (yield 57%).

¹H NMR(500.13MHz,CDCl₃):δ＝7.30-7.33(m,1H),7.43(m,2H),7.50(m,4H),7.57-7.70(m,9H),7.79(d,J＝8.5Hz,2H),8.20(d,J＝7.9Hz,1H),8.39(brs,1H)

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.5mmol (28.8mg), RuPhos0.75mmol (35.0mg), and 0.5mmol (164.1mg) of 4,4' -diaminooctafluorobiphenyl, and the system was subjected to nitrogen substitution. To this solution, 8mL of dioxane was added, 1.05mmol (498.1mg) of 4-bromo-4' - (N-phenylcarbazol-3-yl) -biphenyl was further added, and after stirring for 5 minutes, 0.923mL (1.2mmol) of lhmds1.3mol/L tetrahydrofuran solution was added, and the mixture was heated and stirred in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Finally, the solvent was removed from the fractions collected at 80 ℃ under reduced pressure to obtain 457mg of the objective compound (yield 82%).

¹H NMR(500.13MHz,CDCl₃):δ＝5.94(brs、2H),7.11(brd,2H),7.32(brquin,1H),7.43(brd,2H),7.48-7.51(m,2H),7.60-7.66(m,6H),7.70-7.72(brm,3H),7.80-7.82(m,3H),8.21(brd,2H),8.41(brs,1H)

[ examples 1 to 31]

[ solution 61]

Pd (dppf) Cl was measured in a100 mL reaction flask equipped with a reflux column₂0.45mmol (367.5mg), potassium acetate 45mmol (4416.3mg), 2-bromo-9, 9' -spirobis [ 9H-fluorene]15mmol (5929.5mg) and 16.5mmol (4190.0mg) of bis (pinacolato) diboron were added to the system and the nitrogen was replaced. To this was added 150mL of N, N-dimethylformamide, and after stirring for 5 minutes, the mixture was heated and stirred in a bath at 90 ℃ for 3 hours. Furthermore, the reaction was followed by a chromatography (TLC) method using a small amount of the reaction mixture obtained from the system.

After the reaction mixture was cooled to room temperature, the solvent was removed from the cooled reaction mixture under reduced pressure, the reaction mixture was concentrated, the concentrate was washed with 50mL of ionized water in a separatory funnel, 50mL of chloroform was added thereto, extraction was performed, and the organic layer was collected from the separatory funnel. Then, the recovered organic layer was dried over magnesium sulfate.

Finally, the solvent was removed from the fractions collected under reduced pressure to obtain 1.85g of 9, 9' -spirobis [ 9H-fluoren ] -2-yl-boronic acid pinacol ester (yield 28%).

¹H NMR(500.13MHz,CDCl₃):δ＝1.25(s、12H),6.68(brd,J＝7.5Hz1H),6.71(brd,J＝7.5Hz,2H),7.09(dt,J＝7.5,1.1Hz 2H),7.11(dt,J＝7.5,1.1Hz 1H),7.18(brs、1H),7.35(dt,J＝7.5,1.1Hz 1H),7.36(dt,J＝7.5,1.1Hz 2H),7.33-7.37(m,5H)

[ solution 62]

Pd (PPh) was measured in a 50mL reaction flask equipped with a reflux column₃)₄0.09mmol (104.1mg), 9mmol (359.9mg) of sodium hydroxide, 9' -Spirobis [ 9H-fluorene]3mmol (1327.1mg) of (E) -2-yl-boronic acid pinacol ester and 3.3mmol (1184.7mg) of 4-bromo-4' -iodobiphenyl were added to the system, and nitrogen substitution was performed. To this was added 13.5mL of a mixed solvent of tetrahydrofuran and water (2/1(v/v)), and after stirring for 5 minutes, the mixture was heated and stirred in a bath at 50 ℃ for 5 hours. Furthermore, the reaction was followed by a chromatography (TLC) method using a small amount of the reaction mixture obtained from the system.

Finally, the solvent was removed from the fractions collected under reduced pressure to obtain 2- (4 '-bromobiphenyl-4-yl) -9, 9' -spirobis [ 9H-fluorene ]836.4mg (yield 51%).

¹H NMR(500.13MHz,CDCl₃):δ＝6.73(d,J＝7.6Hz,1H),6.78(d,J＝7.6Hz,2H),6.97(s,1H),7.12(brt,3H),7.36-7.42(m,5H),7.49(s,4H),7.53(d,2H),7.66(dd,J＝7.9,1.8Hz,1H),7.86(d,J＝7.6Hz,2H),7.87(d,J＝7.6Hz,1H),7.92(d,J＝7.9Hz,1H)

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.5mmol (28.8mg), RuPhos0.75mmol (35.0mg), and 0.5mmol (164.1mg) of 4,4' -diaminooctafluorobiphenyl, and the system was subjected to nitrogen substitution. To this was added 8mL of dioxane, and 2- (4 '-bromobiphenyl-4-yl) -9, 9' -spirobis [ 9H-fluorene]1.05mmol (574.9mg), stirred for 5 minutes, then 0.923mL (equivalent to LHMDS1.2mmol) of LHMDS1.3mol/L tetrahydrofuran solution was added, and the mixture was heated and stirred in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Finally, the solvent was removed from the fractions collected at 80 ℃ under reduced pressure to obtain 532mg of the objective compound (yield 86%).

¹H NMR(500.13MHz,CDCl₃):δ＝6.78(brd,2H),6.83(brd,4H),7.05(brm,6H),7.15(brt,6H),7.41(brt,6H),7.54(brm,12H),7.70(brd,2H),7.90(brd,6H),7.95(brd,2H),

¹³C NMR(125.77MHz,CDCl₃):δ＝118.7,120.2,120.3,120.5,122.8,124.3,124.4,126.9,127.1,127.6,127.8,128.0,128.1,135.5,139.4,139.7,140.4,140.6,141.3,141.6,142.0,18.9,149.4,149.8

¹⁹F NMR(470.45MHz,CDCl₃):δ＝-151.41(brd,4F),-140.63(m,4F)

IR (pure) ν to 3387.0(w),3059.1(w),3030.2(w),2953.0(w),2926.0(w),2856.6(w),1653.0(m),1606.7(m),1485.2(s),1446.6(s),1236.4(m),1085.9(m),975.98(m),813.96(s),750.31(s),727.16(s)

A summary of the above examples 1-21 to 1-31 is shown in Table 4.

[ Table 4]

(4) Reaction of pentafluoroaniline with 4,4' -dibromobiphenyl

[ solution 63]

[ examples 1 to 32]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.1mmol (57.5mg), RuPhos0.15mmol (69.8mg), and 1mmol (312.7mg) of 4,4' -dibromobiphenyl were subjected to nitrogen substitution in the system. 8mL of dioxane and 2.4mmol (439.3mg) of pentafluoroaniline were added thereto, and after stirring for 5 minutes, 1.84mL of LHMDS1.3mol/L tetrahydrofuran solution (equivalent to LHMDS2.4mmol) was added, and the mixture was heated and stirred in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography.As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Finally, the solvent was removed from the fractions collected at 80 ℃ under reduced pressure to obtain 451.7mg of the objective compound (yield 58%).

¹H NMR(500.13MHz,DMSO):δ＝6.86(brd,J＝8.1Hz,4H),7.45(brd,J＝8.1Hz,4H),8.32(brs,2H)

¹³C NMR(125.77MHz,DMSO):δ＝116.1,118.1,126.9,132.4,137.0,138.3,142.3,142.7

¹⁹F NMR(470.45MHz,DMSO):δ＝-165.04(brt,2F),-163.81(brt,4F),-148.47(brd,4H)

IR (pure) ν to 3410(m),3029(w),1611(m),1577(w),1517(s),1502(s),1482(s)1446(s),1327(m),1277(m),1238(m),1183(m),1159(m),1136(m),977(s),817(s),779(m),727(m),710 (m); HRMS (ESI)

(5) Reaction of pentafluoroaniline with bromobenzene: influence of alkali

[ solution 64]

[ examples 1 to 33]

The reaction and the post-treatment were carried out in the same manner as in example 1-11 except that pentafluoroaniline (1mmol), bromobenzene (2.4mmol) and LHMDS1.3mol/L tetrahydrofuran solution (1.85 mL, which corresponds to LHMDS2.4mmol) were used, to obtain 179.8mg of the objective compound (yield 69%).

[ examples 1 to 34]

The reaction and the post-treatment were carried out in the same manner as in example 1-11 except that 1.85mL (equivalent to LHMDS2.4mmol) of a pentafluoroamine (2.4mmol), bromobenzene (1mmol) and LHMDS1.3mol/L tetrahydrofuran solution was used, to obtain 193.6mg (yield 75%) of the objective compound.

A summary of examples 1-33 and examples 1-34 is shown in Table 5. From these results, it is found that if an excessive amount of the base is present in the system, the yield tends to decrease.

[ Table 5]

(6) Synthesis of polymers

[ solution 65]

[ example 2-1]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.08mmol (46.0mg), RuPhos0.12mmol (56.0mg), and 4.2mmol (1378.3mg) of 4,4' -diaminooctafluorobiphenyl, and the system was subjected to nitrogen substitution. To this, 8mL of dioxane and 10mmol (943.6mg) of 1, 4-dibromobenzene were added, and after stirring for 5 minutes, 7.1mL of an lhmds1.3mol/L tetrahydrofuran solution (equivalent to lhmds9.2mmol) was added, followed by heating and stirring at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this timeNo significant peak corresponding to the by-product was identified.

After the reaction mixture was cooled to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 100mL of a saturated aqueous ammonium chloride solution and 50mL of ethyl acetate, extraction was performed to leave an organic layer in the separatory funnel, and an aqueous layer was collected. 50mL of a saturated saline solution was put into a separatory funnel, and the remaining organic layer was washed and the aqueous layer and the organic layer were collected. Then, all the collected aqueous layers were combined, placed in a separatory funnel, 30mL of ethyl acetate was added thereto, extraction was performed, the organic layer was collected, all the collected organic layers were combined, and dried over magnesium sulfate.

Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The obtained residue was dissolved in 10mL of tetrahydrofuran, and the resulting solution was added dropwise to 500mL of a mixed solvent of hexane and toluene (2/1(v/v)) to collect a produced solid by filtration, and the obtained filtrate was dried at 80 ℃ under reduced pressure to obtain 0.47g of the objective compound.

¹H NMR(500.13MHz,DMSO):δ＝7.08(brd,J＝7.7Hz,4H),7.56(brd,J＝7.7Hz,4H),8.68(brs,2H)

¹³C NMR(125.77MHz,DMSO):δ＝97.2,117.6,123.9,126.1,127.8,128.5,132.9,140.0,140.7,144.2

¹⁹F NMR(470.45MHz,DMSO):δ＝-148.76(d,J＝17.3Hz,4F),-140.67(s,4F)

IR (pure) v ~ 3421(w),3398(w),3030(w),1652(m),1610(m),1575(w),1482(s),1410(m),1394(m),1291(m),1261(s),1234(s),1183(m),1118(m),1085(s),995(s),973(s),938(m),812(s),721(s)

[ examples 2-2]

Except for using Pd (DBA)₂The reaction and the post-treatment were carried out in the same manner as in example 2-1 except for 0.4mmol (230.0mg) and RuPhos0.6mmol (280.0mg), whereby 1.60g of the objective compound was obtained.

A summary of examples 2-1 and 2-2 is shown in Table 6. As shown in table 6, it is understood that the molecular weight of the obtained polymer can be controlled by changing the amount of the catalyst.

[ Table 6]

[ solution 66]

[ examples 2 to 3]

[ solution 67]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.5mmol (287.5mg), 0.75mmol (350.0mg), 2.5mmol (820.4mg) of 4,4 '-diaminooctafluorobiphenyl, and 2.38mmol (742.9mg) of 4,4' -dibromobiphenyl were subjected to nitrogen substitution. 8mL of dioxane was added thereto, and after stirring for 5 minutes, 7.1mL of LHMDS1.3mol/L tetrahydrofuran solution (equivalent to LHMDS9.2mmol) was added thereto, and the mixture was stirred while heating in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The obtained residue was dissolved in 10mL of tetrahydrofuran, and the resulting solution was added dropwise to 500mL of a mixed solvent of hexane and toluene (2/1(v/v)) to collect a produced solid by filtration, and the obtained filtrate was dried at 80 ℃ under reduced pressure to obtain 1.01g of the objective compound. The obtained polymer had Mw 32000, Mn 15000, and Mw/Mn 2.13, and Δ T5 was 321.6 ℃, and Tg was not observed.

[ examples 2 to 4]

[ solution 68]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.3mmol (172.5mg), RuPhos0.45mmol (210.0mg), 4' -diaminooctafluorobiphenyl 1.5mmol (492.3mg), and 3, 6-dibromo-9-phenylcarbazole 1.43mmol (572.3mg), and the system was subjected to nitrogen substitution. To this was added 8mL of dioxane, and after stirring for 5 minutes, 2.54mL of LHMDS1.3mol/L tetrahydrofuran solution (equivalent to LHMDS3.3mmol) was added, and the mixture was stirred while heating in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The obtained residue was dissolved in 10mL of tetrahydrofuran, and the resulting solution was added dropwise to 500mL of a mixed solvent of hexane and toluene (2/1(v/v)) to collect a produced solid by filtration, and the obtained filtrate was dried at 80 ℃ under reduced pressure to obtain 928mg of the objective compound. The obtained polymer had Mw 12000, Mn 7000 and Mw/Mn 1.71, and Δ T5 was 340.1 ℃, and no Tg was observed.

¹H NMR(500.13MHz,THF):δ＝5.39(d,J＝8.5Hz,2H),5.52(d,J＝8.5Hz,2H),5.62(brs,H),5.80(brs,4H),6.07(d,2H),7.62(brd,J＝8.0Hz,2H),8.06(brs,2H)

¹³C NMR(125.77MHz,THF):δ＝96.7,110.8,113.5,121.4,124.6,126.2,127.7,127.8,128.2,129.1,129.8,130.9,136.0,139.1,139.4,140.2,146.3

¹⁹F NMR(470.45MHz,THF):δ＝-151.34(brd,4F),-145.89(brd,4F)

IR (pure substance)' v ~ ═ 3403(w),3029(w),2927(w),1651(m),1597(w),1483(s),1460(s),1364(w),1328(w),1291(w),1282(w),1211(m),1166(w),1121(w),1080(m),1027(w),994(m),976(s),951(m),939(m),925(w),863(w),757(m),723(s)

[ examples 2 to 5]

[ solution 69]

Pd (DBA) was measured in a 30mL reaction flask equipped with a reflux column₂0.4mmol (230.0mg), RuPhos0.6mmol (280.0mg), 4' -diaminooctafluorobiphenyl 2mmol (656.3mg), and 2, 7-dibromo-9, 9-dimethylfluorene 1.90mmol (670.6mg), and the system was subjected to nitrogen substitution. 8mL of dioxane was added thereto, and after stirring for 5 minutes, 3.2mL of LHMDS1.3mol/L tetrahydrofuran solution (equivalent to LHMDS4.2mmol) was added thereto, and the mixture was stirred while heating in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no correspondence is confirmedA distinct peak in the by-product.

Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The obtained residue was dissolved in 10mL of tetrahydrofuran, and the resulting solution was added dropwise to 500mL of a mixed solvent of hexane and toluene (2/1(v/v)) to collect a formed solid by filtration, followed by drying at 80 ℃ under reduced pressure to obtain 926mg of the objective compound. The obtained polymer had Mw of 20000, Mn of 11000, and Mw/Mn of 1.82, and Δ T5 was 340.1 ℃, and no Tg was observed.

¹H NMR(500.13MHz,THF):δ＝1.52(s,6H),7.02(brd,J＝8.0Hz,2H),7.18(s,2H),7.62(brd,J＝8.0Hz,2H),8.06(brs,2H)

¹³C NMR(125.77MHz,THF):δ＝26.6,46.5,97.1,113.1,117.4,119.3,125.0,127.9,128.7,133.8,139.9,140.7,145.1,154.3

¹⁹F NMR(470.45MHz,THF):δ＝-151.76(brd,4F),-142.20(brd,4F)

IR (pure) v ~ 3423(w),2958(w),2925(w),2859(w),1651(m),1613(w),1587(w),1518(m),1485(s),1464(s),1417(m),1295(m),1259(w),1239(m),1220(w),1195(w),1089(m),995(m),979(s),971(s),809(m),724(m),718(m)

[ examples 2 to 6]

[ solution 70]

At the installation of a reflux towerIn a 30mL reaction flask, Pd (DBA) was measured₂0.3mmol (172.5mg), RuPhos0.45mmol (210.0mg), 4' -diaminooctafluorobiphenyl 1.5mmol (492.3mg), and 9, 10-dibromoanthracene 1.43mmol (480mg) were subjected to nitrogen substitution in the system. To this was added 8mL of dioxane, and after stirring for 5 minutes, 2.54mL of LHMDS1.3mol/L tetrahydrofuran solution (equivalent to LHMDS3.3mmol) was added, and the mixture was stirred while heating in a bath at 110 ℃ for 5 hours (inner temperature: 92 ℃). In the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was followed by liquid chromatography. As the area of the peak attributable to the raw material decreases, the area of the peak attributable to the target increases. At this time, no significant peak corresponding to the by-product was observed.

Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The obtained residue was dissolved in 10mL of tetrahydrofuran, and the resulting solution was added dropwise to 500mL of a mixed solvent of hexane and toluene (2/1(v/v)) to collect a produced solid by filtration, and the filtrate was dried at 80 ℃ under reduced pressure to obtain 928mg of the objective compound. The obtained polymer had Mw 18000, Mn 8100, and Mw/Mn 2.22.

¹H NMR(500.13MHz,DMSO):δ＝7.60(brs,2H),8.31(brs,2H),9.30(brs,1H)

¹³C NMR(125.77MHz,CDCl₃):δ＝123.9,126.4,128.7,129.3,131.3,135.8,137.7,143.5,145.5

¹⁹F NMR(470.53MHz,CDCl₃):δ＝-160.0(brs,4F),-143.2(brs,4F)

IR (pure) v ═ 3361.9(w),1651.1(m),1485.1(s),1435.0(m),1377.2(m),12771.1(w),1178.5(w),1134.1(w),1111.0(w),1045.4(w),970.2(s),950.9(m),763.8(s),723.3(s)

[2] Charge-transporting composition and production of charge-transporting film

[ example 3-1]

In a sample bottle (10mL), 35.9mg of the fluorinated arylamine compound having a naphthyl group represented by the following formula (H1) and 56.2mg of the arylsulfonic acid compound represented by the following formula (D2) synthesized in examples 1 to 24 were weighed, and 3g of tetrahydrofurfuryl alcohol was added and stirred at room temperature until it became uniform, to obtain a solution having a solid content of 3 mass%. The solution was applied to an ITO substrate using a spin coater, and then dried at 80 ℃ for 1 minute under the air, and then fired at 230 ℃ for 15 minutes to prepare a 50nm thick film. As the ITO substrate, a glass substrate having Indium Tin Oxide (ITO) formed on the surface thereof at a film thickness of 50nm was used. On the film, a deposition apparatus (degree of vacuum 4.0X 10) was used^-5Pa) to form an aluminum thin film, resulting in a single-layer element. The evaporation was carried out at an evaporation rate of 0.2 nm/sec. The thickness of the aluminum thin film was set to 80 nm. An arylsulfonic acid compound represented by the following formula (D2) was synthesized according to the method described in international publication No. 2006/025342.

[ solution 71]

[ examples 3-2]

44mg of the fluoroarylamine compound having a triphenylamine group represented by the formula (H2) and 49mg of the arylsulfonic acid compound represented by the formula (D2) synthesized in examples 1 to 26 were weighed in a sample bottle (10mL), and 3g of tetrahydrofurfuryl alcohol was added thereto and stirred at room temperature until the mixture became homogeneous, whereby a solution having a solid content of 3 mass% was obtained. A single-layer element was produced in the same manner as in example 3-1, except that this solution was used.

[ chemical formula 72]

[ examples 3 to 3]

21.6mg of the fluorinated arylamine copolymer having a biphenyl skeleton represented by the following formula (H3) synthesized in example 2 to 3 and 40mg of the arylsulfonic acid compound represented by the above formula (D2) were weighed in a sample bottle (10mL), and 3g of tetrahydrofurfuryl alcohol was added thereto and stirred at room temperature until the mixture became homogeneous, whereby a solution having a solid content of 2 mass% was obtained. A single-layer element was produced in the same manner as in example 3-1, except that this solution was used.

[ solution 73]

[ examples 3 to 4]

In a sample bottle (10mL), 36mg of the fluorinated arylamine copolymer having a phenylcarbazolyl group represented by the following formula (H4) synthesized in example 2 to 4 and 57mg of the arylsulfonic acid compound represented by the above formula (D2) were weighed, and 3g of tetrahydrofurfuryl alcohol was added and stirred at room temperature until the mixture became homogeneous, to obtain a solution having a solid content of 3 mass%. A single-layer element was produced in the same manner as in example 3-1, except that this solution was used.

[ chemical formula 74]

[ examples 3 to 5]

34mg of the fluorinated arylamine copolymer having 9, 9-dimethylfluorenyl group represented by the following formula (H5) synthesized in example 2 to 5 and 59mg of the arylsulfonic acid compound represented by the above formula (D2) were weighed in a sample bottle (10mL), and 3g of tetrahydrofurfuryl alcohol was added and stirred at room temperature until it became uniform to obtain a solution having a solid content of 3 mass%. A single-layer element was produced in the same manner as in example 3-1, except that this solution was used.

[ solution 75]

The current density at a drive voltage of 5V was measured for each of the obtained single-layer devices. The results are shown in Table 7.

[ Table 7]

As shown in table 7, it is understood that the film containing the fluorinated arylamine compound or the polymer of the present invention as a charge transporting substance exhibits good conductivity.

Claims

[ solution 1]

In the formula, R¹Each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R²～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R⁶～R⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or NR⁹ ₂Radical, R⁹Each independently represents an alkyl group having 1 to 20 carbon atoms.

2. The method for producing a fluorinated aromatic secondary amine compound according to claim 1, wherein the catalyst is a palladium 0-valent complex of dibenzylideneacetone, and the ligand is a biphenylphosphine compound represented by the formula (L).

3. The method for producing a fluorinated aromatic secondary amine according to claim 1 or 2, wherein R is¹Each independently is a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the carbon atom bonded to the phosphorus atom is a secondary or tertiary carbon atom.

4. The method for producing a fluorinated aromatic secondary amine according to claim 3, wherein R is¹Both cyclohexyl and tert-butyl.

5. The method for producing a fluorinated aromatic secondary amine according to any one of claims 1 to 4, wherein R is²And R⁵Each independently represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, wherein R is³And R⁴Are each a hydrogen atom, said R⁶～R⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

6. The method for producing a fluorinated aromatic secondary amine according to any one of claims 1 to 5, wherein the biphenylphosphine compound represented by the formula (L) is a biphenylphosphine compound represented by any one of the following formulae (L1) to (L4),

[ solution 2]

Wherein Me means methyl, i-Pr means isopropyl, Cy means cyclohexyl, and t-Bu means t-butyl.

7. The method for producing a fluorinated aromatic secondary amine according to any one of claims 1 to 6, wherein the palladium 0-valent complex of dibenzylidene acetone is bis (dibenzylidene acetone) palladium (0).

8. The method for producing a fluorinated aromatic secondary amine according to any one of claims 1 to 7, wherein the fluorinated aromatic primary amine compound is a fluorinated aromatic primary monoamine compound or diamine compound having 2 or more fluorine atoms in a molecule.

9. The method for producing a fluorinated aromatic secondary amine according to any one of claims 1 to 8, wherein the chlorinated, brominated, or iodinated aromatic hydrocarbon is a monochloroaromatic hydrocarbon or a dichloroaromatic hydrocarbon, a monobromoaromatic hydrocarbon or a dibromoaromatic hydrocarbon, or a monoiodoaromatic hydrocarbon or a diiodoaromatic hydrocarbon.

10. A fluorine-containing aniline derivative represented by the formula (T1) or (T2) excluding compounds represented by the following formulae [1] to [13],

[ solution 3]

In the formula, X²¹¹Represents a 2-valent group represented by any one of formulae (A01-1) to (A09),

[ solution 4]

In the formula, L⁰¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-, fluorene-9, 9-diyl, -NH-or-NZ¹⁰-，

L⁰⁴represents a hydrogen atom, may be represented by Z¹¹Number of carbon atoms substituted1 to 20 alkyl, optionally substituted with Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²A substituted aryl group having 6 to 20 carbon atoms,

a¹²、a¹⁴、a²²、a²⁴、a³²、a³⁴、a⁴²、a⁵²、a⁶²、a⁷²、a⁷⁴、a⁸²、a⁸⁴、a⁹²and a⁹⁴To representZ substituted on the aromatic ring⁰¹～Z⁰⁹The number of (a) or (b) is,

a⁷⁵and a⁷⁶Represents the number of Z' substituted on the aromatic ring,

a⁹¹and a⁹³Each independently of the otherGround is an integer of 1 to 3, a⁹²And a⁹⁴Each independently an integer of 0 to 2, and satisfies a⁹¹+a⁹²3 and a is ≤ 3 and⁹³+a⁹⁴≤3，

[ solution 5]

[ solution 6]

[ solution 7]

In the formula, L¹¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-, fluorene-9, 9-diyl, -NH-or-NZ¹⁰⁰-，

Z¹³²represents a fluorine atom, a chlorine atom or a bromine atom,

Ar¹each independently represents an aryl group having 6 to 20 carbon atoms,

Ar²represents a single bond or an arylene group having 6 to 20 carbon atoms,

[ solution 8]

In the formula, b¹¹、b²¹、b²³、b³¹、b³³、b⁴¹、b⁵¹、b⁶¹、b⁷¹、b⁷³、b⁸¹、b⁸³、b⁹¹And b⁹³Represents the number of fluorine atoms substituted in the aromatic ring,

b⁷⁵and b⁷⁶Represents the number of Z' substituted on the aromatic ring,

L⁰¹～L⁰⁴Z' and Z⁰¹～Z⁰⁷The same meaning as described above is indicated,

Y²²¹represents a 2-valent group represented by any one of formulae (D01-1) to (D21),

[ solution 9]

[ solution 10]

[ solution 11]

[ solution 12]

In the formula, Ar³Each independently represents an arylene group having 6 to 20 carbon atoms, L¹¹～L¹⁴、Z¹⁰¹～Z¹²¹And Ar¹The same meaning as described above is indicated,

[ solution 13]

11. The fluoroaniline derivative according to claim 10, wherein said X is²¹¹Is a 2-valent group represented by the formula (A02).

12. The fluoroaniline derivative according to claim 11, wherein said X is²¹¹Is a 2-valent group represented by the following formula (A02-1):

[ solution 14]

In the formula, a²¹～a²⁴And Z⁰²The same meanings as described above are indicated.

13. The fluoroaniline derivative according to any one of claims 10 to 12, wherein Y is²¹¹And Y²¹²Are the same 1-valent groups.

14. The fluoroaniline derivative of claim 13, wherein said Y is²¹¹And Y²¹²Are each a 1-valent group represented by any one of the formulae (B01), (B02), (B04), (B08), and (B18).

15. The fluoroaniline derivative of claim 10, wherein said Y is²²¹Is a 2-valent group represented by the formula (D02).

16. The fluoroaniline derivative of claim 15, wherein said Y is²²¹Is a 2-valent group represented by the following formula (D02-1):

[ solution 15]

17. The fluoroaniline derivative of claim 10, 15, or 16, wherein X is²²¹And X²²²Are the same 1-valent groups.

18. The fluoroaniline derivative of claim 17, wherein X is²²¹And X²²²All are 1-valent groups represented by the above formula (C01).

[ solution 16]

[ solution 17]

L⁰⁴represents a hydrogen atom, may be represented by Z¹¹A substituted C1-20 alkyl group optionally substituted by Z¹¹Substituted alkenyl of 2-20 carbon atoms or may be substituted by Z¹²Substituted aryl of 6-20 carbon atomsThe base group is a group of a compound,

a⁷⁵and a⁷⁶Represents the number of Z' substituted on the aromatic ring,

a⁹¹and a⁹³Each independently an integer of 1 to 3, a⁹²And a⁹⁴Each independently an integer of 0 to 2, and satisfies a⁹¹+a⁹²3 and a is ≤ 3 and⁹³+a⁹⁴≤3，

[ solution 18]

[ solution 19]

[ solution 20]

[ solution 21]

In the formula, L¹¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-, fluorene-9, 9-diyl, -NH-or-NZ⁰²-，

Z¹³²represents a fluorine atom, a chlorine atom or a bromine atom,

Ar¹each independently represents an aryl group having 6 to 20 carbon atoms,

Ar³each independently represents an arylene group having 6 to 20 carbon atoms.

20. The polymer of claim 19, wherein said X²¹¹Is a 2-valent group represented by the formula (A02).

21. The polymer of claim 20, wherein said X²¹¹Is a 2-valent group represented by the following formula (A02-1),

[ solution 22]

22. A polymer according to any one of claims 19 to 21, wherein Y is²²¹Is a 2-valent group represented by any one of the above formulae (D02), (D17) and (D19).

23. A charge transporting material comprising the aniline derivative according to any one of claims 10 to 18.

24. A charge transporting material comprising the polymer according to any one of claims 19 to 22.

25. A charge transporting composition comprising the charge transporting material according to claim 23 or 24, and an organic solvent.

26. The charge transport composition of claim 25 comprising a dopant species.

27. A charge transport film obtained from the charge transport composition according to claim 25 or 26.

28. An electronic component comprising the charge transporting thin film according to claim 27.

29. An organic electroluminescent element comprising the charge transporting thin film according to claim 27.

30. The organic electroluminescent element according to claim 29, wherein the charge-transporting thin film is a hole-injecting layer or a hole-transporting layer.